CN111170510A - Method for treating arsenic-containing wastewater and solidifying arsenic - Google Patents
Method for treating arsenic-containing wastewater and solidifying arsenic Download PDFInfo
- Publication number
- CN111170510A CN111170510A CN202010066157.XA CN202010066157A CN111170510A CN 111170510 A CN111170510 A CN 111170510A CN 202010066157 A CN202010066157 A CN 202010066157A CN 111170510 A CN111170510 A CN 111170510A
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- China
- Prior art keywords
- arsenic
- liquid
- wastewater
- calcium
- slag
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 178
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims abstract description 174
- 239000002351 wastewater Substances 0.000 title claims abstract description 92
- 238000000034 method Methods 0.000 title claims abstract description 59
- UYZMAFWCKGTUMA-UHFFFAOYSA-K iron(3+);trioxido(oxo)-$l^{5}-arsane;dihydrate Chemical compound O.O.[Fe+3].[O-][As]([O-])([O-])=O UYZMAFWCKGTUMA-UHFFFAOYSA-K 0.000 claims abstract description 61
- 239000013078 crystal Substances 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 230000001590 oxidative effect Effects 0.000 claims abstract description 19
- 230000002378 acidificating effect Effects 0.000 claims abstract description 17
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 13
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 12
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 12
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 12
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 12
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims abstract description 11
- 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 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 9
- 239000002244 precipitate Substances 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims description 86
- 239000002893 slag Substances 0.000 claims description 69
- 238000001556 precipitation Methods 0.000 claims description 59
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 40
- 238000001914 filtration Methods 0.000 claims description 33
- 239000003054 catalyst Substances 0.000 claims description 27
- GSYZQGSEKUWOHL-UHFFFAOYSA-N arsenic calcium Chemical compound [Ca].[As] GSYZQGSEKUWOHL-UHFFFAOYSA-N 0.000 claims description 25
- 239000002002 slurry Substances 0.000 claims description 22
- 229910001385 heavy metal Inorganic materials 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 229910052742 iron Inorganic materials 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 14
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 14
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 14
- 239000004571 lime Substances 0.000 claims description 14
- 239000003638 chemical reducing agent Substances 0.000 claims description 13
- 230000007935 neutral effect Effects 0.000 claims description 13
- 239000007800 oxidant agent Substances 0.000 claims description 13
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 12
- 239000000920 calcium hydroxide Substances 0.000 claims description 12
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 12
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000292 calcium oxide Substances 0.000 claims description 12
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 10
- 238000006386 neutralization reaction Methods 0.000 claims description 10
- 235000019738 Limestone Nutrition 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 239000006028 limestone Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 7
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000004064 recycling Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000007711 solidification Methods 0.000 claims description 6
- 230000008023 solidification Effects 0.000 claims description 6
- BMWMWYBEJWFCJI-UHFFFAOYSA-K iron(3+);trioxido(oxo)-$l^{5}-arsane Chemical compound [Fe+3].[O-][As]([O-])([O-])=O BMWMWYBEJWFCJI-UHFFFAOYSA-K 0.000 claims description 5
- 238000001338 self-assembly Methods 0.000 claims description 5
- 229910017251 AsO4 Inorganic materials 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims description 4
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 235000015165 citric acid Nutrition 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 2
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- 239000010842 industrial wastewater Substances 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- FZGIHSNZYGFUGM-UHFFFAOYSA-L iron(ii) fluoride Chemical compound [F-].[F-].[Fe+2] FZGIHSNZYGFUGM-UHFFFAOYSA-L 0.000 claims description 2
- SHXXPRJOPFJRHA-UHFFFAOYSA-K iron(iii) fluoride Chemical compound F[Fe](F)F SHXXPRJOPFJRHA-UHFFFAOYSA-K 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910001511 metal iodide Inorganic materials 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- RMBBSOLAGVEUSI-UHFFFAOYSA-H Calcium arsenate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-][As]([O-])([O-])=O.[O-][As]([O-])([O-])=O RMBBSOLAGVEUSI-UHFFFAOYSA-H 0.000 abstract description 10
- 229940103357 calcium arsenate Drugs 0.000 abstract description 10
- 239000011575 calcium Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052791 calcium Inorganic materials 0.000 abstract description 5
- AQLMHYSWFMLWBS-UHFFFAOYSA-N arsenite(1-) Chemical compound O[As](O)[O-] AQLMHYSWFMLWBS-UHFFFAOYSA-N 0.000 abstract description 4
- 238000011161 development Methods 0.000 abstract description 3
- 238000009827 uniform distribution Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 14
- 230000009466 transformation Effects 0.000 description 13
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 5
- 238000003723 Smelting Methods 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- 150000002505 iron Chemical class 0.000 description 3
- 239000008267 milk Substances 0.000 description 3
- 210000004080 milk Anatomy 0.000 description 3
- 235000013336 milk Nutrition 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- XPDICGYEJXYUDW-UHFFFAOYSA-N tetraarsenic tetrasulfide Chemical compound S1[As]2S[As]3[As]1S[As]2S3 XPDICGYEJXYUDW-UHFFFAOYSA-N 0.000 description 3
- UNMYWSMUMWPJLR-UHFFFAOYSA-L Calcium iodide Chemical compound [Ca+2].[I-].[I-] UNMYWSMUMWPJLR-UHFFFAOYSA-L 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 229940046413 calcium iodide Drugs 0.000 description 2
- 229910001640 calcium iodide Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000001112 coagulating effect Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- UGYZDRNYHSBEDB-UHFFFAOYSA-L hydrogen arsorate;manganese(2+) Chemical compound [Mn+2].O[As]([O-])([O-])=O UGYZDRNYHSBEDB-UHFFFAOYSA-L 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 238000013048 microbiological method Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 150000003839 salts Chemical class 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
- MHUWZNTUIIFHAS-XPWSMXQVSA-N 9-octadecenoic acid 1-[(phosphonoxy)methyl]-1,2-ethanediyl ester Chemical compound CCCCCCCC\C=C\CCCCCCCC(=O)OCC(COP(O)(O)=O)OC(=O)CCCCCCC\C=C\CCCCCCCC MHUWZNTUIIFHAS-XPWSMXQVSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N L-glucitol Chemical compound OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- VETKVGYBAMGARK-UHFFFAOYSA-N arsanylidyneiron Chemical compound [As]#[Fe] VETKVGYBAMGARK-UHFFFAOYSA-N 0.000 description 1
- 125000001870 arsonato group Chemical group O=[As]([O-])([O-])[*] 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229940047047 sodium arsenate Drugs 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
Classifications
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- 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
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- 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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
- C02F1/705—Reduction by metals
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- 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
- C02F2001/007—Processes including a sedimentation step
-
- 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
- C02F2101/103—Arsenic compounds
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention discloses a method for treating arsenic-containing wastewater and solidifying arsenic, which comprises the steps of separating and enriching arsenic in the arsenic-containing wastewater in the form of calcium arsenate or/and calcium arsenite precipitate, oxidizing the obtained arsenic-enriched substance in ferric sulfate or ferrous sulfate solution, and solidifying the arsenic in the form of scorodite crystals through normal-pressure reaction or pressurized hydrothermal reaction or normal-pressure hydrothermal reaction, wherein the obtained scorodite crystals have complete crystal grain development and uniform distribution, and have stable structure under acidic conditions. The method has the advantages of high operation efficiency, good arsenic fixing effect, convenient operation, low arsenic curing treatment cost and the like, and is suitable for industrial application of harmless treatment of arsenic-containing wastewater.
Description
Technical Field
The invention belongs to the field of environmental protection, and particularly relates to a method for treating arsenic-containing wastewater and solidifying arsenic.
Background
As is a toxic and harmful element, the direct discharge of the arsenic-containing wastewater can cause environmental pollution. Therefore, it is necessary to treat the arsenic-containing waste water. The prior treatment method of arsenic-containing wastewater mainly comprises the following steps: neutralization precipitation, coagulation precipitation, pyrolusite precipitation, sulfide precipitation, and scorodite.
The neutralization precipitation method is that lime or limestone is added into the arsenic-containing waste water to precipitate arsenic in the form of calcium arsenate or/and calcium arsenite, and calcium-arsenic slag and precipitated liquid are obtained by filtration. The method has the advantages of simple process, convenient operation and low treatment cost, and has the defects of high solubility of calcium salt of arsenic, poor stability of the obtained calcium-arsenic slag and easy secondary pollution.
The coagulating sedimentation method uses lime as neutralizing agent and iron salt as coagulant, and adds lime and iron salt into arsenic-containing waste water simultaneously to make arsenic precipitate and separate out, and then filters them to obtain coagulating sedimentation slag and liquid after precipitation. The method has the advantages of good arsenic removal effect and large slag amount, and the obtained coagulation sedimentation slag is unstable under the acidic condition and cannot meet the related requirements of GB 5085.3-2007.
The pyrolusite method is pyrolusite (MnO)2) As oxidant, trivalent arsenic in waste water is oxidized into pentavalent arsenic under heating condition, lime is then added to neutralize, calcium arsenate and manganese arsenate are precipitated and separated out, and mixed filter residue of calcium arsenate and manganese arsenate and precipitated liquid are obtained through filtering. The method has good arsenic precipitation effect, but the obtained mixed filter residue has poor qualitative property and is easy to cause secondary pollution.
The sulfide precipitation method is that a vulcanizing agent is added into arsenic-containing waste water to precipitate arsenic in the form of arsenic sulfide, and arsenic sulfide slag and a liquid after the vulcanization are obtained by filtration. The method has good arsenic precipitation effect, but H exists in the sulfuration process2S gas is generated and needs to be purified, and arsenic sulfide slag is slowly oxidized when contacting with air, so that secondary pollution is easily caused.
Therefore, the method only solves the problem of arsenic pollution in the wastewater, but does not solve the problems of water reuse (zero discharge of wastewater) after wastewater treatment, harmless treatment of the obtained secondary arsenic-containing substances and the like, namely the method does not completely solve the problem of arsenic pollution.
As is well known, scorodite (FeAsO)4·2H2O) is the most stable and least toxic compound of all arsenic-containing species. Therefore, the secondary arsenic-containing substances generated by treating the arsenic-containing wastewater are converted into scorodite to completely solve the problem of arsenic pollution. The scorodite method is a novel chemical precipitation arsenic removal method developed in recent years. According to the method, the ferric salt reacts with arsenic in the wastewater to generate scorodite, and the arsenic in the wastewater is converted into scorodite crystals for storage by utilizing the characteristics of low scorodite solubility and leaching toxicity and high stability under acidic and neutral conditions, so that the aim of safe disposal is fulfilled. The scorodite method comprises a hydrothermal method, a normal pressure method and a microbiological method:
the hydrothermal method is a method for preparing scorodite by mixing arsenic-containing wastewater and iron salt under the condition that the pH value is 0.8-2, placing the mixture in an autoclave, and carrying out hydrothermal reaction under the conditions of high temperature and high pressure. The scorodite prepared by the hydrothermal method has the advantages of complete grain development, uniform distribution, light particle agglomeration and the like. However, the method needs to be carried out under the conditions of high temperature and high pressure, so that the energy consumption is high, the processing capacity of the pressure container is limited, the processed liquid also contains 0.5-1.5 g/L of As, the arsenic removal efficiency is only 92-96%, and the method is not suitable for popularization and application in industrial production.
The normal pressure method is to heat the mixed solution of arsenic-containing wastewater and ferric salt at the constant temperature of 70-95 ℃ under the normal pressure, the pH value is 0.8-2, and the mixture is stirred for 6-8 hours to prepare the scorodite. Compared with a hydrothermal method, the method is simple to operate and low in cost, but the crystallinity and stability of the synthesized scorodite are poor, similar to the hydrothermal method, the dearsenization is incomplete, the dearsenization efficiency is only 92-96%, and the method is not suitable for popularization and application in industrial production.
The microbiological method is characterized in that naturally-existing or artificially-cultured strains are added to oxidize Fe (II) and As (III), and then the reaction is carried out by adjusting conditions such As reaction temperature, initial pH value, iron-arsenic molar ratio and the like to generate scorodite crystals, so that arsenic in the wastewater is fixed, and the purpose of purifying the wastewater is achieved. The method is economically feasible, but the strain culture requirement is high, the arsenic fixing operation period of the microorganism is long, and the efficiency is low.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a method for treating arsenic-containing wastewater and solidifying arsenic, which has the advantages of high operating efficiency, good arsenic-solidifying effect and convenient operation.
The invention relates to a method for treating arsenic-containing wastewater and solidifying arsenic, which comprises the following steps:
the method comprises the following steps: neutralizing and deacidifying
When the arsenic-containing wastewater is acidic arsenic-containing wastewater, lime or limestone is directly added into the acidic arsenic-containing wastewater, the mixture is stirred and neutralized to pH 2-3, free acid in the acidic arsenic-containing wastewater is removed, and filtering is carried out to obtain neutralized deacidified residue I with the content of As being less than or equal to 0.1% and deacidified liquid I, or reducing agent and catalyst I or reducing agent are firstly added into the acidic arsenic-containing wastewater, after the As (V) is reduced to As (III), lime or limestone is added, the mixture is stirred and neutralized to pH 2-3, free acid in the mixture is removed, and neutralized deacidified residue II with the content of As being less than or equal to 0.05% and deacidified liquid II are obtained through filtering;
when the arsenic-containing wastewater is neutral or alkaline arsenic-containing wastewater, directly entering the step II, or adding a reducing agent and a catalyst I or a reducing agent into the neutral or alkaline arsenic-containing wastewater to reduce As (V) into As (III) to obtain reduced liquid, and then entering the step II;
the catalyst I is a compound capable of accelerating the reduction of As (V) into As (III);
step two: arsenic precipitation enrichment
Adding calcium oxide or calcium hydroxide into neutral or alkaline arsenic-containing wastewater or the reduced liquid obtained in the step I or the deacidified liquid II obtained in the step I to precipitate and enrich arsenic and heavy metals in the wastewater, and filtering to obtain mixed precipitate slag and precipitated liquid I, or
Adding calcium oxide or calcium hydroxide into neutral or alkaline arsenic-containing wastewater or the reduced liquid obtained in the step one or the deacidified liquid I or the deacidified liquid II obtained in the step one for pre-neutralization to ensure that heavy metals in the wastewater are preferentially precipitated and separated out, filtering to obtain heavy metal-enriched slag, then continuously adding calcium oxide or calcium hydroxide to ensure that As in the wastewater is precipitated and enriched, and filtering to obtain arsenic-calcium precipitated slag and precipitated liquid II;
step three: arsenic solidification treatment
Adding water into the mixed precipitation slag or the arsenic-calcium precipitation slag obtained in the step two to prepare slurry, adding ferrous sulfate or/and ferric sulfate, and adding an oxidant and at least one of a catalyst II and a scorodite seed crystal, wherein the catalyst II can promote Fe3+Ions with AsO4 3-And (3) forming a compound of scorodite crystals by ion combination self-assembly, converting arsenic in the slurry into scorodite crystals to be solidified under the condition that the pH value is 1-5, filtering to obtain filter residues containing the scorodite crystals and a converted liquid, and returning the converted liquid to be continuously used as a slurry of mixed precipitation residues or arsenic-calcium precipitation residues.
The invention relates to a method for treating arsenic-containing wastewater and solidifying arsenic, which comprises the following step one, wherein the concentration of As in the arsenic-containing wastewater is 0.1-100 g/L, and H+The ion concentration is 5 to 5 x 10-14mol/L。
The invention relates to a method for treating arsenic-containing wastewater and solidifying arsenic, wherein in the first step, a reducing agent is SO2Or H2SO3Or scrap iron, reducing agent is added according to 1-3 times of the theoretical amount required by reducing As (V) into As (III), and acidic or alkaline substances are added to adjust H in the arsenic-containing wastewater+The ion concentration is 0.01 to 1.5mol/L, and the reaction is carried out for 0.25 to 25 hours at the temperature of 0 to 65 ℃.
The invention relates to a method for treating arsenic-containing wastewater and solidifying arsenic, wherein an acidic substance is at least one of sulfuric acid, hydrochloric acid and nitric acid; the alkaline substance is at least one of lime, limestone, sodium hydroxide, sodium carbonate and sodium bicarbonate.
In the first step, the catalyst I is soluble metal iodide, more preferably one of calcium iodide, sodium iodide and potassium iodide, and the addition amount of the catalyst I is 0.01-0.00001% of the mass of arsenic in the wastewater.
In the second step, the arsenic precipitation enrichment refers to that calcium oxide or calcium hydroxide is added into neutral or alkaline arsenic-containing wastewater or the reduced liquid obtained in the first step or the deacidified liquid I or the deacidified liquid II obtained in the first step for neutralization until the pH value is 10-13, so that arsenic and heavy metal in the wastewater are precipitated and enriched together, and the mixed precipitation slag and the precipitated liquid I or the deacidified liquid II are obtained through filtration, so that the arsenic precipitation enrichment is performed, and the mixed precipitation slag is obtained through precipitation, and the precipitated liquid I or the deacidified liquid II is obtained through precipitation
Adding calcium oxide or calcium hydroxide into neutral or alkaline arsenic-containing wastewater or the reduced liquid obtained in the step one or the deacidified liquid I or the deacidified liquid II obtained in the step one for pre-neutralization until the pH value is 7-9, so that heavy metals in the wastewater are preferentially precipitated and separated out, filtering to obtain heavy metal-enriched slag, then continuously adding calcium oxide or calcium hydroxide for neutralization until the pH value is 10-13, so that As in the wastewater is precipitated and enriched, and filtering to obtain arsenic-calcium precipitated slag and precipitated liquid II;
the heavy metal is at least one of Cu, Pb, Zn, Sn, Ni, Co, Sb, Bi, Hg, Fe and Mo;
the obtained precipitated liquid I or the precipitated liquid II is directly returned to the process of industrial wastewater production for recycling, or CO is introduced2And adjusting the pH value to 8-9, recycling the reclaimed water, and using the heavy metal enriched slag as a raw material for extracting valuable metals.
Adding water into the mixed precipitation slag or the arsenic calcium precipitation slag obtained in the step two according to a solid-to-liquid ratio of 1: 1-6, stirring and slurrying to obtain slurry, adding a solid or solution of ferrous sulfate or/and ferric sulfate according to 1-2 times of the theoretical amount of arsenic in the slurry converted into scorodite, adding an oxidant according to 1-3 times of the theoretical amount of As (III) oxidized into As (V) and Fe (II) oxidized into Fe (III), adding at least one of a catalyst II and scorodite seed crystals, reacting at the temperature of 25-95 ℃ for 2-8 hours at the pH of 1-5, and combining the arsenic with the iron to perform a normal pressure reaction to convert the arsenic into scorodite crystals, or performing a normal pressure reaction on the arsenic and the iron to convert the arsenic into scorodite crystals, or performing a reaction on the arsenic calcium precipitation slag obtained in the step three
Adding water into the mixed precipitation slag or the arsenic-calcium precipitation slag obtained in the second step according to a solid-to-liquid ratio of 1: 1-3, stirring and slurrying to obtain slurry, adding a solid or a solution of ferrous sulfate or/and ferric sulfate once according to a theoretical amount of 1-2 times of scorodite of arsenic in the slurry, adding an oxidant according to a theoretical amount of 1-3 times of As (III) oxidized into As (V) and Fe (II) oxidized into Fe (III), adding at least one of a catalyst II and scorodite seed crystals, performing a pressure reaction at a temperature of 105-150 ℃ for 1-3 hours at a pH of 1-5, and combining the arsenic and the iron to convert into scorodite crystals through a pressure hydrothermal reaction, or performing a pressure hydrothermal reaction on the arsenic-calcium precipitation slag to obtain scorodite crystals
Adding water into the mixed precipitation slag or arsenic calcium precipitation slag obtained in the second step according to a solid-to-liquid ratio of 1: 1-3, stirring and slurrying to obtain slurry, adding a solid or solution of ferrous sulfate or/and ferric sulfate once according to a ratio of 1-2 times of the theoretical amount of scorodite obtained by converting arsenic in the slurry into arsenic, adding an oxidant according to a ratio of 1-3 times of the theoretical amount of As (III) oxidized into As (V) and Fe (II) oxidized into Fe (III) oxidized into the oxidant, stirring for 0.25-1.5 h at room temperature, filtering to obtain filtrate and filter residue, directly returning the filtrate to continue to be used As the slurrying liquid of the mixed precipitation slag or arsenic calcium precipitation slag, adding the obtained filter residue into a solution or a melt of sodium hydrogen sulfate according to a ratio of 1: 1-5, adding a catalyst II or/and a scorodite seed crystal, and reacting for 1-3 h at normal pressure at 110-310 ℃, so that amorphous ferric arsenate is converted into a scorodite crystal through a normal pressure thermal reaction.
The invention relates to a method for treating arsenic-containing wastewater and solidifying arsenic, wherein an oxidant refers to a compound capable of oxidizing As (III) into As (V) and oxidizing Fe (II) into Fe (III), and preferably at least one of air, oxygen, ozone, chlorine, hydrogen peroxide, sodium hypochlorite, sodium chlorate, sodium persulfate, manganese dioxide and potassium permanganate.
The invention relates to a method for treating arsenic-containing wastewater and solidifying arsenic, which comprises the third step, wherein a catalyst II is at least one selected from calcium chloride, ferric chloride, ferrous chloride, calcium fluoride, ferric fluoride, ferrous fluoride, citric acid, oxalic acid and tartaric acid, and the mass concentration of the catalyst II in slurry is 1-0.0001%.
According to the method for treating and solidifying arsenic-containing wastewater, the precipitation rate of arsenic reaches 99.78%, and all precipitated arsenic is solidified in the form of scorodite. The obtained scorodite has complete and uniform crystal grain growth and stable structure under an acidic condition, and meets the relevant requirements of GB 5085.3-2007.
The invention relates to a method for treating arsenic-containing wastewater and solidifying arsenic, which has the following basic principle:
As(V)+2e＝As(III) (1)
2AsO3 3-+3Ca2+＝Ca3(AsO3)2↓ (2)
Ca3(AsO3)2+3FeSO4+6H2O＝3CaSO4·2H2O↓+3Fe2++2AsO3 3-(3)
Ca3(AsO3)2+Fe2(SO4)3+6H2O＝3CaSO4·2H2O↓+2Fe3++2AsO3 3-(4)
Fe2+–e＝Fe3+(5)
AsO3 3-+H2O–2e＝AsO4 3-+2H+(6)
Fe3++AsO4 3-+2H2O＝FeAsO4·2H2O↓ (7)
compared with the prior art, the invention has the following advantages and effects:
1. the method comprises the steps of enriching arsenic and curing arsenic, firstly adding calcium into the wastewater to enrich arsenic, and then carrying out scorodite curing treatment on the obtained arsenic-enriched slag, so that the removal rate of arsenic in the wastewater is improved to more than 99% from 92-96% of the traditional scorodite curing process, the precipitation rate of arsenic in the wastewater reaches 99.78%, and all precipitated arsenic is cured in the form of scorodite.
2. The invention skillfully utilizes the synergistic effect of the catalyst II and gypsum (calcium sulfate) generated in the arsenic-enriched slag transformation process, so that the temperature of arsenic-enriched slag transformed into scorodite by iron-adding transformation self-assembly is reduced, the reaction time is shortened, the obtained scorodite has complete crystal grain development and uniform distribution, and the scorodite has a stable structure under an acidic condition.
3. According to the invention, the sodium bisulfate solution or the melt is used as a medium for self-assembly of the scorodite, so that the temperature for synthesizing the scorodite under normal pressure is increased from 70-95 ℃ to 110-310 ℃, the conversion time is shortened from 5-8 h of the traditional process to 1-3 h, the efficiency of arsenic solidification in the form of scorodite is greatly improved, and the cost for treating arsenic solidification treatment by arsenic-containing wastewater is obviously reduced.
Drawings
FIG. 1 is an XRD spectrum of the transformed slag obtained in example 1 of the present invention.
Detailed Description
The invention will now be further described with reference to the following examples, which are intended to illustrate the invention but not to limit it further.
Example 1
Washing arsenic-containing wastewater by 5m by using smelting flue gas3Adding calcium iodide into the solution under stirring-The ion concentration is 0.002mg/L, and H is used2SO3As reducing agents, using I-Reducing As (V) into As (III) by using ions As a catalyst, reacting at room temperature for 0.5h, adding limestone powder, adjusting the pH value of the solution to 2.7, and filtering to obtain a calcium sulfate filter cake containing 0.03 percent of As and deacidified solution; stirring the deacidified liquid, adding lime milk, adjusting the pH value to 8.1, stirring at room temperature for 1h, filtering to separate heavy metal precipitates, continuously adding the lime milk, adjusting the pH value to 12, stirring at room temperature for 0.5h to precipitate arsenic in the heavy metal precipitates, filtering to obtain arsenic-calcium precipitation slag with the As content of 35.87% and a precipitated liquid, and directly returning the precipitated liquid to the smoke washing process for recycling. Adding water into the obtained arsenic-calcium precipitation slag according to the solid-to-liquid ratio of 1:4g/mL for slurrying, adding ferrous sulfate according to the arsenic-to-iron molar ratio of 1:1.1, adding 1/1000 scorodite seed crystal according to the mass ratio of the slurry, carrying out forced air oxidation at 85 ℃ for 5 hours to convert arsenic in the arsenic-calcium precipitation slag into scorodite to be solidified, and filtering to obtain conversion slag and conversion liquid; the pH value of the obtained liquid after transformation is 6.5, the As content is 1.5mg/L, and the liquid after transformation returns to be continuously used As the transformation liquid of the arsenic-calcium precipitation slag; the XRD test result of the obtained transformation slag is shown in figure 1, and the stability of the transformation slag meets the relevant requirements of GB 5085.3-2007; the results of the arsenic enrichment experiments are shown in Table 1, wherein the precipitation rate of arsenic is 99.78%.
Table 1 results of the experiment for enriching arsenic in the washing wastewater of smelting off-gas in example 1, g/L
Example 2
Washing arsenic-containing wastewater by 3m by using smelting flue gas3Stirring and adding limestone powder, adjusting the pH value of the solution to 2.5, filtering to obtain a calcium sulfate filter cake containing 0.1 percent of As and a neutralized liquid, stirring and adding lime milk into the neutralized liquid, adjusting the pH value to 12.5, stirring at room temperature for 1.5 hours to precipitate arsenic and heavy metal in the neutralized liquid, filtering to obtain mixed precipitation slag and a precipitated liquid, and returning the precipitated liquid to reclaimed water for recycling. Adding water into the obtained mixed precipitation slag according to the solid-liquid ratio of 1:2g/mL, pulping in a pressure reaction kettle, adjusting the pH value to 4.5 by using dilute sulfuric acid, adding ferrous sulfate according to the arsenic/iron molar ratio of 1:1.2, adding hydrogen peroxide according to the theoretical amount of 1.5 times of the amount of As (III) oxidized into As (V) and Fe (II) oxidized into Fe (III), performing pressurized reaction at 135 ℃ for 3 hours to ensure that arsenic and iron in the mixed precipitation slag are combined and converted into scorodite to be solidified, and filtering to obtain conversion slag and conversion liquid; the obtained liquid after transformation contains 0.5mg/L of As, and the liquid after transformation returns to be continuously used As the transformation liquid of the mixed precipitation slag; the stability of the obtained transformation slag meets the relevant requirements of GB 5085.3-2007; the results of the enrichment experiments with arsenic are shown in Table 2, wherein the precipitation rate of arsenic is 99.78%.
Table 2 Experimental results of arsenic enrichment in the waste water from washing of smelting flue gas in example 2, g/L
Example 3
Taking 3L of sodium arsenate solution with the As concentration of 35.8g/L obtained in the regeneration process of copper electrolyte indirect self-purification load accelerant, stirring at 95 ℃, adding lime for causticization, filtering to obtain calcium arsenate-containing precipitated slag and a post-arsenic removal solution, returning the post-arsenic removal solution to be continuously used As a regeneration solution of the load accelerant, adding water into the calcium arsenate-containing precipitated slag according to the solid-to-liquid ratio of 1:2g/mL for slurrying, adding sulfuric acid for adjusting the pH value to 2.5, adding ferric sulfate according to the arsenic/iron molar ratio of 1:1.15, stirring to convert arsenic in the calcium arsenate-containing precipitated slag into amorphous ferric arsenate for precipitation, filtering to obtain filter residue and filtrate, returning the filtrate to be continuously used As a transformation solution of the calcium arsenate precipitated slag, adding the filter residue into a sodium bisulfate melt with the temperature of 65 ℃ according to the solid-to-liquid ratio of 1:2g/mL, reacting at 160 ℃ under normal pressure for 2.5h to convert the amorphous ferric arsenate into allite, and adding water to the obtained scorodite-containing filter residue for leaching, returning the formed filtrate and washing water to be continuously used as the transformation liquid of amorphous ferric arsenate, wherein the stability of the scorodite-containing filter residue meets the relevant requirements of GB 5085.3-2007.
Example 4
500g of a mixture of 28.31 percent As-containing calcium arsenate and calcium arsenite obtained by purifying arsenic-containing wastewater is added with water according to a solid-to-liquid ratio of 1:4g/mL for slurrying, sulfuric acid is added for adjusting the pH value to 6.5, ferrous sulfate is added according to an arsenic/iron molar ratio of 1:1.2, 1g of citric acid and 0.5g of ammonium fluoride are added As catalysts, oxygen is introduced at 1atm, the reaction is carried out at 45 ℃ for 6h, the arsenic and the iron in the mixture are combined and converted into scorodite through self-assembly to be solidified, the conversion slag and the conversion liquid are obtained through filtration, the conversion liquid is returned to be continuously used As the conversion liquid of the mixture of the calcium arsenate and the calcium arsenite, the conversion slag is a mixture of gypsum and scorodite, and the stability of the conversion slag meets the relevant requirements of GB 5085.3-2007.
Claims (10)
1. A method for treating arsenic-containing wastewater and solidifying arsenic is characterized by comprising the following steps:
the method comprises the following steps: neutralizing and deacidifying
When the arsenic-containing wastewater is acidic arsenic-containing wastewater, lime or limestone is directly added into the acidic arsenic-containing wastewater, the mixture is stirred and neutralized to pH 2-3, free acid in the acidic arsenic-containing wastewater is removed, and filtering is carried out to obtain neutralized deacidified residue I with the content of As being less than or equal to 0.1% and deacidified liquid I, or reducing agent and catalyst I or reducing agent are firstly added into the acidic arsenic-containing wastewater, after the As (V) is reduced to As (III), lime or limestone is added, the mixture is stirred and neutralized to pH 2-3, free acid in the mixture is removed, and neutralized deacidified residue II with the content of As being less than or equal to 0.05% and deacidified liquid II are obtained through filtering;
when the arsenic-containing wastewater is neutral or alkaline arsenic-containing wastewater, directly entering the step II, or adding a reducing agent and a catalyst I or a reducing agent into the neutral or alkaline arsenic-containing wastewater to reduce As (V) into As (III) to obtain reduced liquid, and then entering the step II;
the catalyst I is a compound capable of accelerating the reduction of As (V) into As (III);
step two: arsenic precipitation enrichment
Adding calcium oxide or calcium hydroxide into neutral or alkaline arsenic-containing wastewater or the reduced liquid obtained in the step I or the deacidified liquid II obtained in the step I to precipitate and enrich arsenic and heavy metals in the wastewater, and filtering to obtain mixed precipitate slag and precipitated liquid I, or
Adding calcium oxide or calcium hydroxide into neutral or alkaline arsenic-containing wastewater or the reduced liquid obtained in the step one or the deacidified liquid I or the deacidified liquid II obtained in the step one for pre-neutralization to ensure that heavy metals in the wastewater are preferentially precipitated and separated out, filtering to obtain heavy metal-enriched slag, then continuously adding calcium oxide or calcium hydroxide to ensure that As in the wastewater is precipitated and enriched, and filtering to obtain arsenic-calcium precipitated slag and precipitated liquid II;
step three: arsenic solidification treatment
Adding water into the mixed precipitation slag or the arsenic-calcium precipitation slag obtained in the step two to prepare slurry, adding ferrous sulfate or/and ferric sulfate, and adding an oxidant and at least one of a catalyst II and a scorodite seed crystal, wherein the catalyst II can promote Fe3+Ions with AsO4 3-And (3) forming a compound of scorodite crystals by ion combination self-assembly, converting arsenic in the slurry into scorodite crystals to be solidified under the condition that the pH value is 1-5, filtering to obtain filter residues containing the scorodite crystals and a converted liquid, and returning the converted liquid to be continuously used as a slurry of mixed precipitation residues or arsenic-calcium precipitation residues.
2. The method for treating arsenic solidification treatment of arsenic-containing wastewater as claimed in claim 1, wherein: in the first step, the As concentration in the arsenic-containing wastewater is 0.1-100 g/L, H+The ion concentration is 5 to 5 x 10-14mol/L。
3. The method of claim 1, wherein the arsenic wastewater is treated and arsenic is solidified by: in the first step, the reducing agent is SO2Or H2SO3Or scrap iron, reducing agent is added according to 1-3 times of the theoretical amount required by reducing As (V) into As (III), and acidic or alkaline substances are added to adjust H in the arsenic-containing wastewater+The ion concentration is 0.01 to 1.5mol/L, and the reaction is carried out for 0.25 to 25 hours at the temperature of 0 to 65 ℃.
4. The method of claim 3, wherein the arsenic wastewater is treated and arsenic is solidified by: the acidic substance is at least one selected from sulfuric acid, hydrochloric acid and nitric acid; the alkaline substance is at least one of lime, limestone, sodium hydroxide, sodium carbonate and sodium bicarbonate.
5. The method of claim 1, wherein the arsenic wastewater is treated and arsenic is solidified by: in the first step, the catalyst I is soluble metal iodide, and the addition amount of the catalyst I is 0.01-0.00001% of the mass of arsenic in the wastewater.
6. The method of claim 1, wherein the arsenic wastewater is treated and arsenic is solidified by: in the second step, the arsenic precipitation enrichment refers to adding calcium oxide or calcium hydroxide into neutral or alkaline arsenic-containing wastewater or the reduced liquid obtained in the first step or the deacidified liquid I or the deacidified liquid II obtained in the first step for neutralization until the pH value is 10-13, so that the arsenic and heavy metal in the wastewater are precipitated and enriched together, and filtering to obtain mixed precipitation slag and the precipitated liquid I, or
Adding calcium oxide or calcium hydroxide into neutral or alkaline arsenic-containing wastewater or the reduced liquid obtained in the step one or the deacidified liquid I or the deacidified liquid II obtained in the step one for pre-neutralization until the pH value is 7-9, so that heavy metals in the wastewater are preferentially precipitated and separated out, filtering to obtain heavy metal-enriched slag, then continuously adding calcium oxide or calcium hydroxide for neutralization until the pH value is 10-13, so that As in the wastewater is precipitated and enriched, and filtering to obtain arsenic-calcium precipitated slag and precipitated liquid II;
the heavy metal is at least one of Cu, Pb, Zn, Sn, Ni, Co, Sb, Bi, Hg, Fe and Mo;
the obtained precipitated liquid I or the precipitated liquid II is directly returned to the technical process of arsenic-containing industrial wastewater production for recycling, or CO is introduced2And adjusting the pH value to 8-9, recycling the reclaimed water, and using the heavy metal enriched slag as a raw material for extracting valuable metals.
7. The method of claim 1, wherein the arsenic wastewater is treated and arsenic is solidified by: in the third step, the arsenic solidification treatment process comprises the steps of adding water into the mixed precipitation slag or the arsenic calcium precipitation slag obtained in the second step according to the solid-to-liquid ratio of 1: 1-6, stirring and slurrying to obtain slurry, adding solid or solution of ferrous sulfate or/and ferric sulfate according to 1-2 times of theoretical amount of scorodite of conversion of arsenic in the slurry, adding oxidant according to 1-3 times of theoretical amount of arsenic in the slurry for oxidation of As (III) into As (V) and Fe (II) into Fe (III), adding at least one of catalyst II and scorodite seed crystal, reacting at the temperature of 25-95 ℃ for 2-8 hours at the pH of 1-5, and enabling the arsenic in the slurry and the iron to be combined and react under normal pressure to convert into scorodite crystals, or reacting at the temperature of 25-95 ℃ for 2-8 hours
Adding water into the mixed precipitation slag or arsenic-calcium precipitation slag obtained in the second step according to a solid-to-liquid ratio of 1: 1-3, stirring and slurrying to obtain slurry, simultaneously adding a solid or solution of ferrous sulfate or/and ferric sulfate once according to a theoretical amount of 1-2 times of scorodite of arsenic in the slurry, adding an oxidant according to a theoretical amount of 1-3 times of As (III) oxidized into As (V) and Fe (II) oxidized into Fe (III), adding at least one of a catalyst II and scorodite seed crystal, performing a pressure reaction at 105-150 ℃ for 1-3 hours at a pH of 1-5, and combining the arsenic and the iron to convert the arsenic and the iron into scorodite crystals through a pressure hydrothermal reaction, or performing a pressure hydrothermal reaction on the arsenic-calcium precipitation slag at 105-150 ℃ for 1-3 hours
And (2) adding water into the mixed precipitation slag or arsenic-calcium precipitation slag obtained in the second step according to a solid-to-liquid ratio of 1: 1-3, stirring and slurrying to obtain slurry, simultaneously adding a solid or solution of ferrous sulfate or/and ferric sulfate once according to a theoretical amount of 1-2 times of scorodite, oxidizing As (III) into As (V) and Fe (II) into Fe (III), adding an oxidant according to a theoretical amount of 1-3 times of the theoretical amount of Fe (III), stirring at room temperature for 0.25-1.5 h, filtering to obtain filtrate and filter residue, directly returning the filtrate to continue to be used As a slurrying liquid of the mixed precipitation slag or arsenic-calcium precipitation slag, adding the obtained filter residue into a solution or a melt of sodium hydrogen sulfate according to a solid-to-liquid ratio of 1: 1-5, adding a catalyst II or/and a scorodite seed crystal, and reacting at normal pressure of 110-310 ℃ for 1-3 h, so that amorphous ferric arsenate is often subjected to hydrothermal reaction and converted into a scorodite.
8. The method of claim 1, wherein the arsenic wastewater is treated and arsenic is solidified by: in the third step, the oxidant refers to a compound capable of oxidizing As (III) into As (V) and oxidizing Fe (II) into Fe (III).
9. The method of claim 8, wherein the arsenic wastewater is treated and arsenic is solidified by: in the third step, the oxidant is at least one selected from air, oxygen, ozone, chlorine, hydrogen peroxide, sodium hypochlorite, sodium chlorate, sodium persulfate, manganese dioxide and potassium permanganate.
10. The method of claim 1, wherein the arsenic wastewater is treated and arsenic is solidified by: in the third step, the catalyst II is at least one selected from calcium chloride, ferric chloride, ferrous chloride, calcium fluoride, ferric fluoride, ferrous fluoride, citric acid, oxalic acid and tartaric acid, and the mass concentration of the catalyst II in the slurry is 1-0.0001%.
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| CN112028331A (en) * | 2020-09-15 | 2020-12-04 | 昆明理工大学 | Method for treating arsenic-containing waste acid by using hematite and manganese sand |
| CN112047811A (en) * | 2020-08-24 | 2020-12-08 | 锡矿山闪星锑业有限责任公司 | Arsenic removal method for ethylene glycol mother liquor containing arsenic |
| CN112108485A (en) * | 2020-08-25 | 2020-12-22 | 锡矿山闪星锑业有限责任公司 | Harmless treatment method of arsenate |
| CN112317513A (en) * | 2020-10-26 | 2021-02-05 | 湖南有色金属研究院 | Method for stabilizing arsenic-containing waste residue |
| CN114716063A (en) * | 2022-04-07 | 2022-07-08 | 锡矿山闪星锑业有限责任公司 | Treatment method of antimony-arsenic-containing wastewater |
| CN114836636A (en) * | 2022-05-24 | 2022-08-02 | 江西理工大学 | Method for separating arsenic from arsenic-containing alkali liquor and recovering alkali |
| CN115304105A (en) * | 2022-09-14 | 2022-11-08 | 中南大学 | Method for hydrothermally solidifying arsenic-rich crystal |
| CN115385477A (en) * | 2022-08-23 | 2022-11-25 | 长春黄金研究院有限公司 | Method for removing arsenic in contaminated acid |
| CN115448372A (en) * | 2022-09-14 | 2022-12-09 | 中南大学 | Method for hydrothermal oxygen pressure solidification of high-arsenic crystal by composite ferric salt |
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| CN112047811B (en) * | 2020-08-24 | 2023-10-27 | 锡矿山闪星锑业有限责任公司 | Arsenic removal method for arsenic-containing ethylene glycol mother liquor |
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| CN114836636A (en) * | 2022-05-24 | 2022-08-02 | 江西理工大学 | Method for separating arsenic from arsenic-containing alkali liquor and recovering alkali |
| CN115385477A (en) * | 2022-08-23 | 2022-11-25 | 长春黄金研究院有限公司 | Method for removing arsenic in contaminated acid |
| CN115304105A (en) * | 2022-09-14 | 2022-11-08 | 中南大学 | Method for hydrothermally solidifying arsenic-rich crystal |
| CN115304105B (en) * | 2022-09-14 | 2023-09-22 | 中南大学 | Method for thermally curing arsenic-rich crystals |
| CN115448372B (en) * | 2022-09-14 | 2023-09-22 | 中南大学 | Method for solidifying high-arsenic crystal by using composite iron salt through hydrothermal oxygen pressure |
| CN115448372A (en) * | 2022-09-14 | 2022-12-09 | 中南大学 | Method for hydrothermal oxygen pressure solidification of high-arsenic crystal by composite ferric salt |
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