CN116177779B - Recycling method of titanium white wastewater - Google Patents
Recycling method of titanium white wastewater Download PDFInfo
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- CN116177779B CN116177779B CN202211580611.9A CN202211580611A CN116177779B CN 116177779 B CN116177779 B CN 116177779B CN 202211580611 A CN202211580611 A CN 202211580611A CN 116177779 B CN116177779 B CN 116177779B
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 238000000034 method Methods 0.000 title claims abstract description 81
- 239000002351 wastewater Substances 0.000 title claims abstract description 70
- 235000010215 titanium dioxide Nutrition 0.000 title claims abstract description 60
- 238000004064 recycling Methods 0.000 title claims abstract description 31
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 47
- 239000002253 acid Substances 0.000 claims abstract description 36
- 238000000605 extraction Methods 0.000 claims abstract description 36
- 238000001816 cooling Methods 0.000 claims abstract description 34
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 30
- 238000002425 crystallisation Methods 0.000 claims abstract description 18
- 230000008025 crystallization Effects 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 238000005374 membrane filtration Methods 0.000 claims abstract description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 122
- 239000000243 solution Substances 0.000 claims description 73
- 239000000706 filtrate Substances 0.000 claims description 59
- 238000001914 filtration Methods 0.000 claims description 57
- 239000007788 liquid Substances 0.000 claims description 47
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 45
- 239000010440 gypsum Substances 0.000 claims description 40
- 229910052602 gypsum Inorganic materials 0.000 claims description 40
- 239000012074 organic phase Substances 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 239000012528 membrane Substances 0.000 claims description 32
- 239000007787 solid Substances 0.000 claims description 26
- 229910052719 titanium Inorganic materials 0.000 claims description 23
- 239000010936 titanium Substances 0.000 claims description 23
- 238000003763 carbonization Methods 0.000 claims description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 21
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 20
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 20
- 239000012452 mother liquor Substances 0.000 claims description 20
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 19
- 229910052782 aluminium Inorganic materials 0.000 claims description 19
- 239000000292 calcium oxide Substances 0.000 claims description 19
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 18
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 18
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 18
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 18
- 238000001471 micro-filtration Methods 0.000 claims description 18
- 229910021645 metal ion Inorganic materials 0.000 claims description 17
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 235000006408 oxalic acid Nutrition 0.000 claims description 15
- 239000002244 precipitate Substances 0.000 claims description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 238000001223 reverse osmosis Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- -1 aluminum ions Chemical class 0.000 claims description 13
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical class [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 13
- 239000011777 magnesium Substances 0.000 claims description 13
- 238000000926 separation method Methods 0.000 claims description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 10
- 239000010941 cobalt Substances 0.000 claims description 10
- 229910017052 cobalt Inorganic materials 0.000 claims description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 10
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 8
- VODGJKZAAVKBAL-UHFFFAOYSA-L diazanium;manganese(2+);disulfate Chemical class [NH4+].[NH4+].[Mn+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VODGJKZAAVKBAL-UHFFFAOYSA-L 0.000 claims description 8
- 239000003085 diluting agent Substances 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 8
- 150000004692 metal hydroxides Chemical class 0.000 claims description 8
- 229910052706 scandium Inorganic materials 0.000 claims description 8
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 8
- 238000004945 emulsification Methods 0.000 claims description 7
- 239000003350 kerosene Substances 0.000 claims description 7
- 239000012071 phase Substances 0.000 claims description 7
- 239000002893 slag Substances 0.000 claims description 7
- 239000001038 titanium pigment Substances 0.000 claims description 7
- HSEYYGFJBLWFGD-UHFFFAOYSA-N 4-methylsulfanyl-2-[(2-methylsulfanylpyridine-3-carbonyl)amino]butanoic acid Chemical compound CSCCC(C(O)=O)NC(=O)C1=CC=CN=C1SC HSEYYGFJBLWFGD-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 6
- 238000000354 decomposition reaction Methods 0.000 claims description 6
- 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 claims description 6
- 230000003472 neutralizing effect Effects 0.000 claims description 6
- UGLUPDDGTQHFKU-UHFFFAOYSA-M [NH4+].S(=O)(=O)([O-])[O-].[Mg+] Chemical class [NH4+].S(=O)(=O)([O-])[O-].[Mg+] UGLUPDDGTQHFKU-UHFFFAOYSA-M 0.000 claims description 5
- 239000001569 carbon dioxide Substances 0.000 claims description 5
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 5
- OMMFSGNJZPSNEH-UHFFFAOYSA-H oxalate;scandium(3+) Chemical compound [Sc+3].[Sc+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O OMMFSGNJZPSNEH-UHFFFAOYSA-H 0.000 claims description 5
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 4
- 235000019738 Limestone Nutrition 0.000 claims description 4
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 4
- 125000005586 carbonic acid group Chemical group 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 229940062993 ferrous oxalate Drugs 0.000 claims description 4
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 4
- 239000004571 lime Substances 0.000 claims description 4
- 239000006028 limestone Substances 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229910001456 vanadium ion Inorganic materials 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- MZZBPDKVEFVLFF-UHFFFAOYSA-N cyanazine Chemical compound CCNC1=NC(Cl)=NC(NC(C)(C)C#N)=N1 MZZBPDKVEFVLFF-UHFFFAOYSA-N 0.000 claims description 3
- 238000005286 illumination Methods 0.000 claims description 3
- 239000004033 plastic Substances 0.000 claims description 3
- 239000002699 waste material Substances 0.000 abstract description 22
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052717 sulfur Inorganic materials 0.000 abstract description 7
- 239000011593 sulfur Substances 0.000 abstract description 7
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- 235000012255 calcium oxide Nutrition 0.000 description 15
- 230000029087 digestion Effects 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000011084 recovery Methods 0.000 description 8
- 239000011575 calcium Substances 0.000 description 7
- 230000002829 reductive effect Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 230000001804 emulsifying effect Effects 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910017053 inorganic salt Inorganic materials 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 229910052720 vanadium Inorganic materials 0.000 description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- DCNGHDHEMTUKNP-UHFFFAOYSA-L diazanium;magnesium;disulfate Chemical class [NH4+].[NH4+].[Mg+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DCNGHDHEMTUKNP-UHFFFAOYSA-L 0.000 description 3
- 239000003337 fertilizer Substances 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 3
- 239000000347 magnesium hydroxide Substances 0.000 description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000005955 Ferric phosphate Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
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- 229940032958 ferric phosphate Drugs 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 2
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000012047 saturated solution Substances 0.000 description 2
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000020 calcium bicarbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical group CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- CJMZLCRLBNZJQR-UHFFFAOYSA-N ethyl 2-amino-4-(4-fluorophenyl)thiophene-3-carboxylate Chemical group CCOC(=O)C1=C(N)SC=C1C1=CC=C(F)C=C1 CJMZLCRLBNZJQR-UHFFFAOYSA-N 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
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- 238000003672 processing method Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Abstract
The invention relates to a recycling method of titanium dioxide wastewater, belonging to the technical field of titanium dioxide waste acid wastewater treatment. The invention solves the technical problem of providing a recycling method of titanium white wastewater. The method comprises the steps of pre-neutralization, membrane filtration or deep neutralization, concentration, cooling crystallization, extraction and neutralization. The invention adopts a specific method to comprehensively recycle various valuable metal elements and sulfur elements from the titanium white wastewater with low acid concentration, the wastewater can reach the discharge standard after being treated, and meanwhile, each element in the wastewater can be separated and effectively utilized. Not only the titanium white wastewater is treated, but also the elements in the wastewater are utilized in a high quality. The method has the advantages of simple process, low cost, low energy consumption, no corrosion to equipment and industrialized application.
Description
Technical Field
The invention relates to a recycling method of titanium dioxide wastewater, belonging to the technical field of titanium dioxide waste acid wastewater treatment.
Background
The yield of titanium dioxide exceeds 300 ten thousand tons/year. Because the titanium ore in China is not suitable for adopting the chloridizing process, the production process of titanium dioxide by the sulfuric acid process is mainly adopted. A large amount of titanium white waste acid is produced as a byproduct in the sulfuric acid method titanium dioxide production process. In the production process of titanium dioxide by the sulfuric acid method, 3.9-4.3 tons of 98% sulfuric acid is consumed for each ton of titanium dioxide production, 7-11 tons of waste acid with the concentration W (H 2SO4) =about 20% is produced, and 30-50 tons of waste water with the concentration lower than 5% sulfuric acid is produced. The waste acid and the waste water contain a large amount of valuable metal elements (iron, scandium, vanadium, manganese, cobalt, titanium, magnesium, aluminum and the like).
At present, the industry basically adopts a concentration recycling technology, and the acid wastewater is changed into a titanium gypsum deslagging field for storage after lime neutralization. Valuable metal elements in waste acid and waste water are not recycled, but the problems of serious blockage of equipment pipelines, high titanium gypsum impurity content, inconvenience in utilization and the like are caused in the concentration process. On the premise of realizing the concentration and recycling of waste acid, about 9 tons of gypsum slag (5 tons on a dry basis and 4 tons of water) are produced as byproducts per ton of titanium dioxide, the sulfuric acid recovery rate is low, and the acid recovery rate is basically about 85%.
The waste acid concentration has the following problems: 1. the equipment is severely corroded, and the failure rate is high. 2. The cost of concentrating waste acid is high, and the steam consumption is large. 3. The content of iron impurities precipitated in the waste acid concentration process is high, the amount of entrained concentrated waste acid is large, the waste acid is difficult to comprehensively utilize, and only the waste acid can be neutralized and discharged. 4. The content of valuable metal elements such as iron, scandium, vanadium, manganese, cobalt, titanium, magnesium, aluminum and the like in the gypsum slag is too high to realize the comprehensive utilization of the gypsum slag, and the gypsum slag is also a huge waste of various valuable metal resources. Therefore, a method for recycling titanium white wastewater is needed.
The Chinese patent application No. 201210270170.2 discloses a method for enriching rare elements of rare earth from sulfuric acid process titanium white waste liquid and preparing white gypsum, and the pH value of the waste liquid is neutralized to 0.5-1.5 to form white slurry: the pH of the slurry is finely adjusted to control the pH of the system to be 1.5-3.0, and the white gypsum filter cake and filtrate are obtained after filtration and washing: regulating the filtrate, controlling the pH value to be 5-7, precipitating iron, scandium and vanadium in the filtrate, and filtering to form an enriched filter cake enriched with rare elements of rare earth and an iron-enriched residual liquid: dissolving the enrichment filter cake by using an acid solution to obtain an enrichment solution enriched with rare elements of rare earth and acidolysis residues: and (3) respectively enriching and purifying iron, vanadium and scandium in the enriched liquid by a step-by-step hydrolysis and extraction method. The concentration of sulfuric acid in the titanium white waste liquid treated by the method is 250g/L, and for low-concentration titanium white waste water, the enrichment difficulty is high by adopting the method, and the method cannot comprehensively recycle various metal resources and sulfur in the waste water.
The Chinese patent application number 201510388879.6 discloses a treatment method of titanium white wastewater, which specifically comprises the following steps: 1) Adding quicklime into the sulfuric acid process titanium dioxide wastewater for neutralization treatment and aeration; 2) Adding flocculant into the aerated wastewater to gather and coagulate the dispersive impurities in the wastewater, wherein larger impurities can be precipitated in a buffer water tank, the rest of the impurities enter an ultrafiltration membrane tank together with the wastewater, colloid, insoluble substances, microorganisms and the like in the wastewater are removed from the wastewater after the wastewater is filtered by an ultrafiltration membrane, and the turbidity of the wastewater is reduced to below 0.2NTU to form inorganic salt wastewater; 3) And pressurizing the inorganic salt wastewater by a high-pressure pump to enter a reverse osmosis membrane assembly to remove inorganic salt in the inorganic salt wastewater so as to form qualified industrial water. The method mainly relates to the circulation of water resources, and metallic elements and nonmetallic elements in the wastewater are not effectively recycled.
The invention patent of China with the application number 202111656165.0 discloses a comprehensive utilization method of sulfuric acid process titanium dioxide wastewater, which comprises the following steps: s1, carrying out sectional collection on wastewater generated in a first washing process of the meta-titanic acid, wherein the wastewater is divided into first washing front section water and first washing back section water; s2, filtering the water of the first washing front section through micropores, and then cooling to be less than or equal to 35 ℃; s3, mixing waste acid, titanium concentrate and concentrated sulfuric acid, performing acidolysis reaction to obtain acidolysis reaction solid phase matters, and adding cooled primary washing water to dissolve the acidolysis reaction solid phase matters to obtain titanyl sulfate solution; s4, adding heated first-washing post-stage water after the hydrolysis material is boiled for the second time in the sulfuric acid method titanium dioxide hydrolysis section, and continuously introducing steam into the hydrolysis material to ensure that the temperature of the hydrolysis material is more than 100 ℃. The method only recycles the sulfuric acid in the titanium white wastewater, and does not recycle other elements.
Disclosure of Invention
Aiming at the defects, the technical problem solved by the invention is to provide a recycling method of titanium white wastewater, which comprehensively utilizes various metal and nonmetal resources in the wastewater.
The invention discloses a recycling method of titanium white wastewater, which comprises the following steps:
a. pre-neutralization: adjusting the pH value of the titanium white wastewater to be 1-3, and then filtering and washing to obtain gypsum and filtrate;
b. purifying filtrate: treating the filtrate by adopting a membrane filtration or deep neutralization method to obtain purified liquid;
Wherein the membrane filtration is: a, filtering the filtrate obtained in the step a through a microfiltration membrane, and concentrating through a reverse osmosis membrane to obtain purified liquid;
Depth neutralization is: adjusting the pH value of the filtrate obtained by filtering in the step a to be 10-11, filtering to obtain metal hydroxide precipitate, adding acid into the metal hydroxide precipitate for acidolysis, and filtering to obtain purified liquid; the obtained solid is acid insoluble and gypsum;
c. Concentrating, cooling and crystallizing: b, evaporating and concentrating the purified liquid in the step b to a saturation concentration not lower than 40 ℃, cooling and crystallizing, wherein the cooling temperature range is 5-40 ℃, and carrying out solid-liquid separation to obtain ferrous sulfate heptahydrate and mother liquor;
d. Extraction: c, extracting the mother liquor after solid-liquid separation in the step with an extraction liquid to obtain an organic phase rich in metal ions; the extracting solution is a mixed solution of an extracting agent and a diluting agent, the extracting agent is at least one of P204, P507, cynex and 272, DNNSA, naphthenic acid and tertiary carbonic acid, and the diluting agent is at least one of sulfonated kerosene, cyclohexane and n-butanol; the extraction ratio O/A=0.2:1-6:1, the temperature is 10-70 ℃;
e. And (3) neutralization: and d, neutralizing and filtering the water phase after the extraction in the step to obtain gypsum and filtrate reaching the emission standard.
In one embodiment of the invention, the concentration of sulfuric acid in the titanium dioxide wastewater is 3-5 wt%.
In one embodiment of the invention, in the step a, lime or limestone is used for adjusting the pH value of the titanium white wastewater.
In a specific embodiment of the invention, in the step a, carbon dioxide generated during the adjustment of the pH value is filtered after the carbonization reaction of saturated lime water, the filter residue is light calcium carbonate, and the filtrate is returned for emulsification of calcium oxide.
In a preferred embodiment of the invention, the gypsum obtained in step a, step b or step e is treated by the following method: the gypsum is dried and dehydrated to semi-hydrated gypsum, then is mixed with a reducing agent for reduction and decomposition to obtain calcium oxide and sulfur dioxide, the sulfur dioxide is catalyzed, oxidized and absorbed to obtain 98 percent sulfuric acid, the calcium oxide is emulsified and filtered, the filtrate is saturated lime water, and the filter residue is titanium-containing slag.
In one embodiment of the invention, in step b, the filtrate filtered during deep neutralization is returned to the neutralization of step e, and the solution for adjusting the pH during deep neutralization is the filtrate of calcium oxide emulsification filtration.
In one embodiment of the invention, in the step b, the microfiltration membrane is a plastic membrane, a metal membrane or a ceramic membrane, the aperture of the microfiltration membrane is 0.1-1.0 μm, and the operation pressure of the microfiltration is 0.02-0.2 MPa; the operating pressure of reverse osmosis is lower than 9MPa.
In one embodiment of the invention, the clean water obtained by concentrating the reverse osmosis membrane in the step b and the condensed water obtained by concentrating in the step c are returned to the titanium dioxide production process.
In one embodiment of the invention, in the step d, the organic phase rich in metal ions is subjected to back extraction by different back extraction agents, and the metal ions are separated and recovered.
Preferably, the back extraction method comprises the following steps in sequence:
1) The method comprises the steps of (1) using an ammonium sulfate solution as a stripping solution 1, stripping manganese, magnesium and vanadium ions in an organic phase rich in metal ions to obtain the stripping solution and the organic phase 1, filtering the hot stripping solution, washing the solid to obtain ammonium polyvanadate solid, cooling and crystallizing the filtrate to obtain double salts of magnesium ammonium sulfate and manganese ammonium sulfate, and recycling the crystallization mother liquor as the stripping solution 1;
2) The sulfuric acid solution is used as stripping solution 2 to strip aluminum ions in the organic phase 1 to obtain the organic phase 2 and aluminum-rich sulfuric acid; after enriching aluminum ions in the aluminum-enriched sulfuric acid, adding ammonium sulfate solid, cooling and crystallizing, wherein the cooling temperature is 0-40 ℃, so as to obtain aluminum ammonium sulfate crystals, and the crystallization mother liquor is recycled as stripping liquor 2;
3) The sulfuric acid and the double oxidation mixed solution are used as strip liquor 3 to strip titanium ions in the organic phase 2 to obtain the organic phase 3 and titanium-rich sulfuric acid, the titanium-rich sulfuric acid returns to the titanium pigment production process,
4) And (3) using oxalic acid solution as stripping solution 4, stripping iron, cobalt and scandium in the organic phase 3 to obtain scandium oxalate precipitate, filtering, and obtaining ferrous oxalate solid with low impurity content after filtrate illumination, and carrying out solid-liquid separation, wherein the liquid is cobalt-containing solution, and the solution is recycled as stripping solution 4 after oxalic acid is added.
In one embodiment of the present invention, the concentration of ammonium sulfate in the ammonium sulfate solution is 5 to 40%; in the sulfuric acid solution, the concentration of sulfuric acid is 5-60%; in the mixed solution of sulfuric acid and double oxidation, the concentration of the sulfuric acid is 6mol/L, and the concentration of the hydrogen peroxide is 4wt%; in the oxalic acid solution, the concentration of oxalic acid is 3-30%.
Compared with the prior art, the invention has the following beneficial effects:
The invention adopts a specific method to comprehensively recycle various valuable metal elements and sulfur elements from the titanium white wastewater with low acid concentration, the wastewater can reach the discharge standard after being treated, and meanwhile, each element in the wastewater can be separated and effectively utilized. Not only the titanium white wastewater is treated, but also the elements in the wastewater are utilized in a high quality. The method has the advantages of simple process, low cost, low energy consumption, no corrosion to equipment and industrialized application.
Drawings
FIG. 1 is a process flow diagram of a method for recycling titanium dioxide wastewater according to examples 1 and 2 of the present invention.
FIG. 2 is a process flow diagram of a method for recycling titanium dioxide wastewater in embodiment 3 of the invention.
Detailed Description
The invention discloses a recycling method of titanium white wastewater, which comprises the following steps:
a. Pre-neutralization: regulating the pH value of the titanium white wastewater to be 1-3, and then filtering to obtain gypsum and filtrate;
b. purifying filtrate: treating the filtrate by adopting a membrane filtration or deep neutralization method to obtain purified liquid;
Wherein the membrane filtration is: a, filtering the filtrate obtained in the step a through a microfiltration membrane, and concentrating through a reverse osmosis membrane to obtain purified liquid;
Depth neutralization is: adjusting the pH value of the filtrate obtained by filtering in the step a to be 10-11, filtering to obtain metal hydroxide precipitate, adding acid into the metal hydroxide precipitate for acidolysis, and filtering to obtain purified liquid; the obtained solid is acid insoluble and gypsum;
c. Concentrating, cooling and crystallizing: b, evaporating and concentrating the purified liquid in the step b to a saturation concentration not lower than 40 ℃, cooling and crystallizing, wherein the cooling temperature range is 5-40 ℃, and carrying out solid-liquid separation to obtain ferrous sulfate heptahydrate and mother liquor;
d. Extraction: c, extracting the mother liquor after solid-liquid separation in the step with an extraction liquid to obtain an organic phase rich in metal ions; the extracting solution is a mixed solution of an extracting agent and a diluting agent, the extracting agent is at least one of P204, P507, cynex and 272, DNNSA, naphthenic acid and tertiary carbonic acid, and the diluting agent is at least one of sulfonated kerosene, cyclohexane and n-butanol; the extraction ratio O/A=0.2:1-6:1, the temperature is 10-70 ℃;
e. And (3) neutralization: and d, neutralizing and filtering the water phase after the extraction in the step to obtain gypsum and filtrate reaching the emission standard.
According to the method, sulfur and valuable metal resources in the titanium white wastewater can be comprehensively recycled through pre-neutralization, microfiltration, reverse osmosis membrane concentration, cooling crystallization, re-extraction of crystallization mother liquor and neutralization, and the method is simple, low in energy consumption and free from equipment corrosion.
The method of the present invention can be applied to a titanium white wastewater having a low acid concentration, and in one embodiment of the present invention, the concentration of sulfuric acid in the titanium white wastewater is 3 to 5wt%.
And a step a is preneutralization, the pH value of the titanium white wastewater is regulated to be 1-3, and then the gypsum and filtrate are obtained through filtration.
Methods of adjusting pH commonly used in the art are suitable for use in the present invention. In one embodiment of the invention, lime or limestone is used to adjust the pH of the titanium dioxide wastewater.
Carbon dioxide gas will be generated during the neutralization reaction. The gas may be treated by conventional means, preferably by the following means: carbon dioxide generated during pH value adjustment is subjected to carbonization reaction of saturated lime water, and then is filtered, filter residues are light calcium carbonate, and the filtrate can be used for emulsifying calcium oxide.
The carbonization reaction is to introduce CO 2 into saturated lime water, and a large amount of Ca (OH) 2 is converted into CaCO 3 through the carbonization reaction, so that the state of precipitation is presented; the carbonization reaction mainly affects factors such as carbonization temperature, carbonization time and end point pH, and the end point pH is a key index for measuring whether calcium and magnesium are effectively separated, experiments show that the carbonization temperature is not too high, preferably 35-40 ℃, the carbonization time is controlled by the end point pH, the end point pH cannot be too high or too low, if the pH is too high, the carbonization of Mg (OH) 2 is incomplete, mgO cannot be well removed, if the pH is too low, side reaction (CaCO 3+H2O+CO2＝Ca(HCO3)2) is caused, and the carbonization end point pH is preferably 7.4-7.5.
And filtering after the carbonization reaction is finished to obtain superfine light calcium carbonate precipitate, and drying to obtain a light calcium carbonate product. The granularity of the product obtained by the process is smaller, and agglomeration is easy to occur. A small amount of alcohol can be added in the precipitation process, so that the dispersion effect is better.
The filtration in the step a can be plate-and-frame filter pressing, belt type vacuum filtration, full-automatic vertical filter pressing and the like. After filtration, the obtained filter residue is gypsum, and the filtrate enters the next step of treatment.
In a preferred embodiment of the invention, the gypsum obtained in step a, step b or step e is treated by the following method: drying and dehydrating gypsum to semi-hydrated gypsum, mixing the semi-hydrated gypsum with a reducing agent, carrying out reduction decomposition to obtain calcium oxide and sulfur dioxide, absorbing the sulfur dioxide to obtain 98% sulfuric acid, emulsifying the calcium oxide, filtering, wherein filtrate is saturated lime water, and filter residues are titanium-containing slag.
In a specific embodiment of the present invention, the reducing agent is at least one of sulfur, carbon, or sulfur concentrate.
Emulsification is the digestion experiment of calcium oxide. Water bath heating can be adopted to ensure that the materials are heated uniformly. The experiment is carried out under the same slurry concentration at the same temperature and different water consumption and different temperatures, the temperature range is 20-100 ℃, and the water consumption range is 2-10 times of the mass of the powder. Experiments show that the digestion time is longer but has no effect on the yield when the temperature is too low, and the Ca (OH) 2 yield is reduced when the temperature is too high. When the water consumption for digestion is lower than 6 times of the mass of the powder, the digestion is not thoroughly carried out, the slurry concentration is high, the stirring is difficult, and the subsequent carbonization experiment is difficult to carry out; when the water consumption is higher than 8 times of the powder mass, part of digestion products are dissolved in water, and the yield of the digestion products is reduced. Therefore, the digestion temperature is determined to be 70-90 ℃, and the water consumption is 6-8 times of the mass of the powder.
In one embodiment of the invention, the saturated lime water is returned to the carbonization process of carbon dioxide or to the neutralization reaction of the aqueous phase obtained in the subsequent extraction step.
Step b is a process of purifying the filtrate, and can be performed by membrane filtration or deep neutralization.
The membrane filtration method comprises the following steps: and d, filtering the filtrate in the step a through a microfiltration membrane, and concentrating through a reverse osmosis membrane.
In one embodiment of the invention, the microfiltration membrane is a plastic membrane, a metal membrane or a ceramic membrane, the aperture of the microfiltration membrane is 0.1-1.0 μm, and the operation pressure of the microfiltration is 0.02-0.2 MPa; the operating pressure of reverse osmosis is lower than 9MPa.
In one embodiment of the invention, the clean water obtained by concentrating the reverse osmosis membrane is returned to the titanium dioxide production process.
After reverse osmosis concentration, the solute content in the concentrated solution is 50-100 g/L, and the concentrated solution can be subjected to the next step of concentration, cooling and crystallization.
The depth neutralization method comprises the following steps: adjusting the pH value of the filtrate obtained by filtering in the step a to be 10-11, filtering to obtain metal hydroxide precipitate, adding acid into the metal hydroxide precipitate for acidolysis, and filtering to obtain purified liquid; the resulting solids were acid insoluble and gypsum.
In one embodiment of the invention, in step b, the filtrate filtered during deep neutralization is returned to the neutralization of step e, and the solution for adjusting the pH during deep neutralization is the filtrate of calcium oxide emulsification filtration.
And a, carrying out deep neutralization (pH=10-11) on the filtrate obtained by filtering in the step a, and filtering the filtrate to obtain a neutralized solution in the step e; the solution for adjusting the pH value in the deep neutralization process can be filtered by emulsifying calcium oxide; and c, carrying out acidolysis on the book hydroxide filtered after deep neutralization by using waste acid or waste acid water, filtering to remove acid insoluble substances and gypsum, dehydrating the gypsum, then reducing and decomposing the gypsum, and carrying out the step c on the filtrate.
And c, concentrating, cooling and crystallizing, evaporating and concentrating the purified liquid in the step b to reach a saturation concentration (namely 73.3 g) at 40 ℃, cooling and crystallizing, and separating solid from liquid to obtain ferrous sulfate heptahydrate and mother liquor.
In one embodiment of the invention, the evaporated condensed water is returned to the titanium pigment production process.
In one embodiment of the present invention, the temperature of the cooling crystallization is 10 to 40 ℃.
The crystal obtained by cooling and crystallizing is ferrous sulfate heptahydrate, and can be used for producing ferric phosphate.
The crystallization mother liquor is subjected to subsequent further treatment.
D, extracting the mother liquor in the step c by using an extraction liquid to obtain an organic phase rich in metal ions.
The extracting solution is a mixed solution of an extracting agent and a diluent, wherein the extracting agent is at least one of P204 (the chemical name is di (2-ethylhexyl) phosphate), P507 (the chemical name is 2-ethylhexyl phosphonic acid mono-2-ethylhexyl), cynex272 (the chemical name is di (2, 4-trimethylpentyl) hypophosphorous acid), DNNSA (the chemical name is dinonylnaphthalene sulfonic acid), naphthenic acid and tertiary carbonic acid.
In one embodiment of the invention, the volume ratio of extractant to diluent is 1:1 to 3.
In one embodiment of the present invention, the sulfonated kerosene may employ No. 260 solvent oil.
In one embodiment of the invention, the extraction is performed at a temperature of 10 to 70 ℃ compared to O/a=0.2:1 to 6:1.
In one embodiment of the invention, in step d, the organic phase enriched in metal ions is subjected to back extraction and the metal ions are separated and recovered.
Preferably, the back extraction method comprises the following steps in sequence:
1) The method comprises the steps of using an ammonium sulfate solution as a strip liquor 1, using the ammonium sulfate solution as the strip liquor 1, strip extracting manganese, magnesium and vanadium ions in an organic phase rich in metal ions to obtain the strip liquor and the organic phase 1, filtering the strip liquor while the strip liquor is hot, washing the solid to obtain ammonium polyvanadate solid, cooling and crystallizing the filtrate to obtain double salts of ammonium magnesium sulfate and ammonium manganese sulfate, separating the ammonium magnesium sulfate from the ammonium manganese sulfate under different cooling conditions, wherein the ammonium magnesium sulfate can be directly used as a fertilizer or used for preparing magnesium hydroxide flame retardant, and the ammonium manganese sulfate can be used for preparing high-value products such as high-purity manganese carbonate;
2) The sulfuric acid solution is used as stripping solution 2 to strip aluminum ions in the organic phase 1 to obtain the organic phase 2 and aluminum-rich sulfuric acid; after enriching aluminum ions in the aluminum-enriched sulfuric acid, adding ammonium sulfate solid, cooling and crystallizing, wherein the cooling temperature is 0-40 ℃, so as to obtain aluminum ammonium sulfate crystals, the crystallization mother liquor is used as a back extraction liquor 2 for recycling, the aluminum ammonium sulfate crystals can be used as a precursor raw material for preparing NCA positive electrode materials by a coprecipitation method, and the crystals can also be used for preparing aluminum hydroxide and ammonium sulfate;
3) The sulfuric acid and the double oxidation mixed solution are used as strip liquor 3 to strip titanium ions in the organic phase 2 to obtain the organic phase 3 and titanium-rich sulfuric acid, the titanium-rich sulfuric acid returns to the titanium pigment production process,
4) And (3) back-extracting iron, cobalt and scandium in the organic phase 3 by using oxalic acid solution as a back-extracting solution 4 to obtain scandium oxalate precipitate, wherein the following reaction occurs during the process:
2ScCl3+3H2C2O4＝Sc2(C2O4)3↓+6HCl
And then filtering, drying the obtained solid to scandium oxalate precipitate, and burning to obtain the scandium oxide. The filtrate is irradiated to obtain ferrous oxalate solid, solid-liquid separation is carried out, the liquid is cobalt-containing solution, and oxalic acid is added to be used as back extraction liquid 4 for recycling; the solid can be used as lithium iron phosphate raw material. Because the cobalt oxalate is almost insoluble in water, the back extraction liquid 4 can be cooled or concentrated and crystallized, and the cobalt oxalate is removed after filtering and washing, so that the recycling of the back extraction liquid 4 is realized.
In one embodiment of the present invention, the concentration of ammonium sulfate in the ammonium sulfate solution is not more than that of a saturated solution, preferably 5 to 40%.
The concentration of sulfuric acid in the sulfuric acid solution is 5-60%.
In the sulfuric acid and double oxidation mixed liquid, the acid concentration is 2-10 mol/L, and the hydrogen peroxide concentration is 1-8wt%; preferably, the concentration of sulfuric acid is 6mol/L, and the concentration of hydrogen peroxide is 4wt%.
In the oxalic acid solution, the concentration of oxalic acid is not more than that of the saturated solution, preferably 3 to 30%.
And e, neutralizing, and d, neutralizing and filtering the water phase extracted in the step to obtain gypsum and filtrate reaching the discharge standard.
In one embodiment of the invention, the saturated lime water produced by reductive decomposition of gypsum in step a is neutralized.
The following describes the invention in more detail with reference to examples, which are not intended to limit the invention thereto.
Example 1
The components of the titanium dioxide wastewater adopted in the embodiment are shown in table 1:
TABLE 1
| H2SO4/(g/L) | Total Fe/(g/L) | Al2O3/(g/L) | MgO/(g/L) | V2O5/(g/L) | TiO2/(g/L) | Sc2O3/(g/L) | CoO/(g/L) |
| 38.48 | 6.13 | 1.55 | 1.86 | 0.16 | 0.81 | 0.003 | 0.003 |
The processing method is shown in fig. 1, and specifically comprises the following steps:
1) Pre-neutralization: neutralizing titanium white wastewater with limestone until the pH value is 2 to obtain a pre-neutralization product; and (3) carrying out carbonization reaction on CO 2 generated during neutralization and saturated lime water, and then filtering, wherein filter residues are light calcium carbonate, and the filtrate is reserved.
The carbonization reaction is to introduce CO 2 into saturated lime water, and a large amount of Ca (OH) 2 is converted into CaCO 3 through the carbonization reaction, so that the state of precipitation is presented; while a small amount of Mg (OH) 2 was converted to Mg (HCO 3)2 was present in the solution and CaCO 3 was separated from Mg (HCO 3)2) by filtration to effect separation of calcium and magnesium the carbonization temperature was controlled to 37 ℃ (Mg (pyrolysis temperature of HCO 3)2 is 60 ℃), and the carbonization endpoint pH was 7.4.
And filtering after carbonization to obtain superfine light calcium precipitate, and drying to obtain a light calcium product. The granularity of the product obtained by the process is smaller, and agglomeration is easy to occur. A small amount of alcohol can be added in the precipitation process, so that the dispersion effect is better.
2) And (3) filtering: carrying out plate-frame filter pressing on a pre-neutralization product, carrying out next microfiltration on the obtained filtrate, dehydrating the obtained filter residue which is gypsum, mixing the dehydrated filter residue with sulfur, carrying out reductive decomposition to obtain sulfur dioxide gas and calcium oxide, preparing 98% sulfuric acid from the sulfur dioxide gas, mixing the calcium oxide with the filtrate in the step 1), emulsifying, filtering, wherein the filtrate is saturated lime water, partially returning to the step 1) for carbonization reaction, and returning to the step 8) for neutralization reaction, wherein the other part contains titanium, and titanium resources can be recovered from the filter residue.
Emulsification is the digestion experiment of calcium oxide. Water bath heating can be adopted to ensure that the materials are heated uniformly. The digestion temperature is 80 ℃, and the water consumption is 7 times of the mass of the powder.
3) Microfiltration: and 2) carrying out microfiltration on the filtrate subjected to the pressure filtration in the step 2) by adopting a plastic film, wherein the pore diameter of the plastic film is 0.2 mu m, and the operating pressure is 0.1MPa.
4) Membrane concentration: the liquid after microfiltration is concentrated by a reverse osmosis membrane, the operating pressure is not more than 9MPa, the obtained clean water is returned to the titanium pigment production process, and the solute content in the concentrated liquid after concentration is 50-100 g/L.
5) Concentrating: the concentrated solution is further evaporated and concentrated, condensed water returns to the titanium pigment production process, and after the concentrated solution is concentrated to saturated solubility, the next step of cooling crystallization is carried out.
6) Cooling and crystallizing: cooling the concentrated solution obtained in the step 5) to 20 ℃ for crystallization, and then carrying out solid-liquid separation, wherein the solid is ferrous sulfate heptahydrate, and the ferrous sulfate heptahydrate can be used for producing ferric phosphate; the liquid is crystallization mother liquor.
7) Extraction: extracting the crystallization mother liquor by adopting an extracting solution, wherein the extracting solution is P204+ sulfonated kerosene, and the volume ratio of the P204 to the sulfonated kerosene is 1:2; the extraction phase was carried out at room temperature compared to O/a=2:1, and after extraction, an aqueous phase and an organic phase rich in metal ions were obtained.
8) Back extraction: the method comprises the steps of using 35wt.% ammonium sulfate solution as a stripping solution 1, stripping manganese, magnesium and vanadium ions in an organic phase rich in metal ions, wherein the ratio of the manganese ions to the magnesium ions is A/O=1/2, obtaining a stripping solution and an organic phase 1, filtering the hot stripping solution, washing the solid to obtain ammonium polyvanadate solid, cooling and crystallizing the stripping filtrate to obtain double salts of magnesium ammonium sulfate and manganese ammonium sulfate, separating the magnesium ammonium sulfate from the manganese ammonium sulfate under different cooling conditions, wherein the magnesium ammonium sulfate can be directly used as a fertilizer or used for preparing magnesium hydroxide flame retardant, the manganese ammonium sulfate can be directly used as a fertilizer or used for preparing magnesium hydroxide, aluminum hydroxide and ammonium sulfate, and the crystallization mother liquor can be used as the stripping solution 1 for recycling.
Using sulfuric acid solution with the concentration of 30-35 wt.% as stripping solution 2, and stripping aluminum ions in the organic phase 1, wherein the ratio of the aluminum ions to the organic phase 2 is A/O=1/1, so as to obtain an organic phase 2 and aluminum-rich sulfuric acid; after the aluminum ions in the aluminum-enriched sulfuric acid are enriched, adding ammonium sulfate solid, cooling and crystallizing (cooling temperature is 0-40 ℃) to obtain aluminum ammonium sulfate crystals, recycling the crystallization mother liquor as stripping liquor 2, wherein the aluminum ammonium sulfate crystals can be used as a precursor raw material for preparing NCA positive electrode materials by a coprecipitation method, and the crystals can also be used for preparing aluminum hydroxide and ammonium sulfate.
And (3) taking sulfuric acid and double oxidation mixed liquor as a strip liquor 3, wherein the acidity of the sulfuric acid is 6mol/L, the hydrogen peroxide content is 4wt%, and titanium ions in the strip organic phase 2 are compared with O/A=3:1 to obtain an organic phase 3 and titanium-rich sulfuric acid, and the titanium-rich sulfuric acid is returned to the titanium pigment production process.
Oxalic acid solution with oxalic acid concentration of 10wt.% is used as stripping solution 4, iron, cobalt and scandium in organic phase 3 are stripped, the ratio O/A=1/1, scandium oxalate precipitate is obtained, filtration and filtrate illumination are carried out to obtain ferrous oxalate solid, solid-liquid separation is carried out, the liquid is cobalt-containing solution, after oxalic acid is added, crystallization and filtration are carried out, the solid is cobalt oxalate, and the liquid is used as stripping solution 4 for recycling.
9) And (3) neutralization: the aqueous phase after the extraction of step 7) is neutralized with saturated lime water.
10 Filtering: and 9) filtering the water phase after the neutralization in the step 9), wherein filter residues are gypsum, and the water phase can be returned to the step 2) for reductive decomposition. And the filtrate is discharged after biochemical treatment reaches the discharge standard.
Based on 100kg of wastewater, 3.83kg of light calcium carbonate, 1.9L of 98% sulfuric acid and 2.13kg of ferrous sulfate heptahydrate were obtained, and the recovery rates of the respective elements were measured, and the results are shown in Table 2.
The method for calculating the recovery rate comprises the following steps:
Recovery = amount of each metal ion separated per 100% of the titanium white spent acid.
TABLE 2
Example 2
Referring to the method of example 1, only the extract at the time of extraction in step 7) was changed to p507+ sulfonated kerosene, and the amounts of light calcium carbonate, 98% sulfuric acid and ferrous sulfate heptahydrate obtained were similar to those of example 1, and the recovery rates of the respective elements were measured, and the results are shown in table 2. Therefore, only the extraction and back extraction steps are changed, the yields of light calcium carbonate, 98% sulfuric acid and ferrous sulfate heptahydrate are basically not influenced, and only the yields of other elements are influenced.
Example 3
Referring to the method of example 1, only the step b is changed to the deep neutralization, that is, the filtrate obtained by filtering in the step a is further subjected to the deep neutralization (ph=10 to 11) and then filtered, and the filtered filtrate can be used as the solution neutralized in the step e; the solution for adjusting the pH value in the deep neutralization process can be filtered by emulsifying calcium oxide; and c, carrying out acidolysis on the book hydroxide filtered after deep neutralization by using waste acid or waste acid water, filtering to remove acid insoluble substances and gypsum, dehydrating the gypsum, then reducing and decomposing the gypsum, and carrying out the step c on the filtrate. A specific process flow diagram is shown in fig. 2. The process can further improve the yield of 98% sulfuric acid, and the mother liquor inevitably contains a small amount of metal ions after filtration due to the deep neutralization precipitation reaction, so that the recovery rate of each metal cation is slightly reduced, the recovery rate of each element is shown in Table 2, and the effect of the process on light calcium carbonate is not great.
Claims (10)
1. The recycling method of the titanium white wastewater is characterized by comprising the following steps of:
a. pre-neutralization: adjusting the pH value of the titanium white wastewater to be 1-3, and then filtering and washing to obtain gypsum and filtrate;
b. purifying filtrate: treating the filtrate by adopting a membrane filtration or deep neutralization method to obtain purified liquid;
Wherein the membrane filtration is: a, filtering the filtrate obtained in the step a through a microfiltration membrane, and concentrating through a reverse osmosis membrane to obtain purified liquid;
Depth neutralization is: adjusting the pH value of the filtrate obtained by filtering in the step a to be 10-11, filtering to obtain metal hydroxide precipitate, adding acid into the metal hydroxide precipitate for acidolysis, and filtering to obtain purified liquid; the obtained solid is acid insoluble and gypsum;
c. Concentrating, cooling and crystallizing: b, evaporating and concentrating the purified liquid in the step b to a saturation concentration not lower than 40 ℃, cooling and crystallizing, wherein the cooling temperature range is 5-40 ℃, and carrying out solid-liquid separation to obtain ferrous sulfate heptahydrate and mother liquor;
d. Extraction: c, extracting the mother liquor after solid-liquid separation in the step with an extraction liquid to obtain an organic phase rich in metal ions; the extracting solution is a mixed solution of an extracting agent and a diluting agent, the extracting agent is at least one of P204, P507, cynex and 272, DNNSA, naphthenic acid and tertiary carbonic acid, and the diluting agent is at least one of sulfonated kerosene, cyclohexane and n-butanol; the extraction ratio O/A=0.2:1-6:1, the temperature is 10-70 ℃;
e. And (3) neutralization: and d, neutralizing and filtering the water phase extracted in the step, thus obtaining gypsum, and carrying out biochemical treatment on the filtrate to reach the emission standard.
2. The recycling method of titanium dioxide wastewater according to claim 1, which is characterized in that: the concentration of sulfuric acid in the titanium white wastewater is 3-5 wt%.
3. The recycling method of titanium dioxide wastewater according to claim 1, which is characterized in that: in the step a, lime or limestone is adopted to adjust the pH value of the titanium white wastewater.
4. The recycling method of titanium dioxide wastewater according to claim 1, which is characterized in that: in the step a, carbon dioxide generated during the adjustment of the pH value and saturated lime water are subjected to carbonization reaction, then are filtered, the solid is dried to obtain light calcium carbonate, and the filtrate is returned to be used for emulsification of calcium oxide.
5. The recycling method of titanium dioxide wastewater according to claim 1, which is characterized in that: the gypsum obtained in the step a, the step b or the step e is treated by the following method: the gypsum is dried and dehydrated to semi-hydrated gypsum, then is mixed with a reducing agent for reduction and decomposition to obtain calcium oxide and sulfur dioxide, the sulfur dioxide is catalyzed, oxidized and absorbed to obtain 98 percent sulfuric acid, the calcium oxide is emulsified and filtered, the filtrate is saturated lime water, and the filter residue is titanium-containing slag.
6. The recycling method of titanium dioxide wastewater according to claim 1, which is characterized in that: in the step b, the filtered filtrate is returned to the neutralization in the step e during deep neutralization, and the solution for regulating the pH value during deep neutralization is calcium oxide emulsification and filtration filtrate;
and b, returning the clean water obtained by concentrating the reverse osmosis membrane in the step c and the condensed water obtained by concentrating in the step c to the titanium dioxide production process.
7. The recycling method of titanium dioxide wastewater according to claim 1, which is characterized in that: in the step b, the microfiltration membrane is a plastic membrane, a metal membrane or a ceramic membrane, the aperture of the microfiltration membrane is 0.1-1.0 mu m, and the operation pressure of the microfiltration is 0.02-0.2 MPa; the reverse osmosis operates at a pressure of less than 9 MPa.
8. The recycling method of titanium dioxide wastewater according to claim 1, which is characterized in that: and d, in the step, the organic phase rich in metal ions is subjected to back extraction by different back extractants, and the metal ions are separated and recovered.
9. The recycling method of titanium dioxide wastewater according to claim 8, which is characterized in that: the back extraction method comprises the following steps of:
1) The method comprises the steps of (1) using an ammonium sulfate solution as a stripping solution 1, stripping manganese, magnesium and vanadium ions in an organic phase rich in metal ions to obtain the stripping solution and the organic phase 1, filtering the hot stripping solution, washing the solid to obtain ammonium polyvanadate solid, cooling and crystallizing the filtrate to obtain double salts of magnesium ammonium sulfate and manganese ammonium sulfate, and recycling the crystallization mother liquor as the stripping solution 1;
2) The sulfuric acid solution is used as stripping solution 2 to strip aluminum ions in the organic phase 1 to obtain the organic phase 2 and aluminum-rich sulfuric acid; after enriching aluminum ions in the aluminum-enriched sulfuric acid, adding ammonium sulfate solid, cooling and crystallizing, wherein the cooling temperature is 0-40 ℃, so as to obtain aluminum ammonium sulfate crystals, and the crystallization mother liquor is recycled as stripping liquor 2;
3) The mixed solution of sulfuric acid and hydrogen peroxide is used as strip liquor 3 to strip titanium ions in the organic phase 2 to obtain the organic phase 3 and titanium-rich sulfuric acid, the titanium-rich sulfuric acid returns to the titanium pigment production process,
4) And (3) using oxalic acid solution as stripping solution 4, stripping iron, cobalt and scandium in the organic phase 3 to obtain scandium oxalate precipitate, filtering, and obtaining ferrous oxalate solid after filtrate illumination, and carrying out solid-liquid separation, wherein the liquid is cobalt-containing solution, and the solution is recycled as stripping solution 4 after oxalic acid is added.
10. The recycling method of titanium dioxide wastewater according to claim 9, which is characterized in that: in the ammonium sulfate solution, the concentration of ammonium sulfate is 5-40 wt%; in the sulfuric acid solution, the concentration of sulfuric acid is 5-60 wt%; in the mixed solution of sulfuric acid and hydrogen peroxide, the concentration of sulfuric acid is 6 mol/L, and the concentration of hydrogen peroxide is 4 wt%; in the oxalic acid solution, the concentration of oxalic acid is 3-30 wt%.
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