CN106830244B - 一种从含氟酸性废水中分离回收氟和酸的方法 - Google Patents
一种从含氟酸性废水中分离回收氟和酸的方法 Download PDFInfo
- Publication number
- CN106830244B CN106830244B CN201710109253.6A CN201710109253A CN106830244B CN 106830244 B CN106830244 B CN 106830244B CN 201710109253 A CN201710109253 A CN 201710109253A CN 106830244 B CN106830244 B CN 106830244B
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- China
- Prior art keywords
- fluorine
- acid
- complex
- recovering
- solution
- 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.)
- Expired - Fee Related
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 121
- 239000011737 fluorine Substances 0.000 title claims abstract description 121
- 239000002253 acid Substances 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 47
- 239000002351 wastewater Substances 0.000 title claims abstract description 47
- 230000002378 acidificating effect Effects 0.000 title claims abstract description 30
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000007788 liquid Substances 0.000 claims abstract description 28
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 229960002050 hydrofluoric acid Drugs 0.000 claims abstract description 12
- 238000001556 precipitation Methods 0.000 claims abstract description 12
- 239000008139 complexing agent Substances 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 28
- 239000002244 precipitate Substances 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 11
- 238000000502 dialysis Methods 0.000 claims description 10
- 238000009792 diffusion process Methods 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 239000003929 acidic solution Substances 0.000 claims description 8
- 239000012528 membrane Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 150000002739 metals Chemical class 0.000 claims description 6
- 239000012716 precipitator Substances 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 150000001450 anions Chemical class 0.000 claims description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 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
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 4
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 4
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 4
- 239000000292 calcium oxide Substances 0.000 claims description 4
- 235000012255 calcium oxide Nutrition 0.000 claims description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000002893 slag Substances 0.000 claims description 4
- 235000002639 sodium chloride Nutrition 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- JTNCEQNHURODLX-UHFFFAOYSA-N 2-phenylethanimidamide Chemical compound NC(=N)CC1=CC=CC=C1 JTNCEQNHURODLX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 2
- 229910001626 barium chloride Inorganic materials 0.000 claims description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 2
- UCVMQZHZWWEPRC-UHFFFAOYSA-L barium(2+);hydrogen carbonate Chemical compound [Ba+2].OC([O-])=O.OC([O-])=O UCVMQZHZWWEPRC-UHFFFAOYSA-L 0.000 claims description 2
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 claims description 2
- 229910000020 calcium bicarbonate Inorganic materials 0.000 claims description 2
- 229910000019 calcium carbonate 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
- 235000011148 calcium chloride Nutrition 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 229910000343 potassium bisulfate Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims description 2
- 229910000342 sodium bisulfate 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
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 2
- 238000004065 wastewater treatment Methods 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 239000003463 adsorbent Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 238000009388 chemical precipitation Methods 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 230000001112 coagulating effect Effects 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000000701 coagulant Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000536 complexating effect Effects 0.000 description 3
- 150000002221 fluorine Chemical class 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000002156 adsorbate Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000006115 defluorination reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009297 electrocoagulation Methods 0.000 description 2
- 239000008394 flocculating agent Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005272 metallurgy Methods 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- XWROUVVQGRRRMF-UHFFFAOYSA-N F.O[N+]([O-])=O Chemical compound F.O[N+]([O-])=O XWROUVVQGRRRMF-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 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
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- -1 ammonium ions Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 230000003311 flocculating effect Effects 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- RHDUVDHGVHBHCL-UHFFFAOYSA-N niobium tantalum Chemical compound [Nb].[Ta] RHDUVDHGVHBHCL-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 235000019794 sodium silicate Nutrition 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
Classifications
-
- 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
- C02F2101/00—Nature of the contaminant
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Abstract
一种从含氟酸性废水中分离回收氟和酸的方法,是先往含氟酸性废水中加络氟剂,使其中的氟转化成络氟酸,然后加入络氟酸沉淀剂,使其中的氟以络氟酸盐形式沉淀析出,过滤得络氟酸盐沉淀物和沉氟后液,所得络氟酸盐沉淀物直接作产品销售或用作氟化合物的生产原料,沉氟后液中的酸进一步回收利用,具有工艺简单,操作简便,废水处理成本低,资源综合利用率高,环境友好等优点。
Description
技术领域
本发明属于化工及冶金领域,具体涉及一种从含氟酸性废水中分离回收氟和酸的方法。
背景技术
氟及其化合物广泛用于化工、冶金、玻璃、电镀、电子、化肥、农药等领域,随着现代化工业的发展,含氟废水的排放量越来越大。含氟废水,尤其是酸性含氟废水的腐蚀性强危害大,含氟废水的治理越来越受到人们的重视。
国内外关于含氟废水的处理方法有很多,如化学沉淀法、混凝沉淀法、吸附法、反渗透法、离子交换法、电渗析法、活性炭除氟、电凝聚法等。在这些方法中,离子交换法对废水的水质要求较严格,且成本费用高;活性炭除氟需要使用大量活性炭,运行成本也很高;反渗透法和电凝聚法的耗电量大、装置复杂、设备昂贵。对于以达标排放为主要目标的含氟工业水处理来说,只有化学沉淀法、混凝沉淀法及吸附法能接受。
化学沉淀法的工艺过程是:向含氟废水中加化学药剂使其中的氟转化成氟化物沉淀或氟化物与生成的沉淀物共沉淀,然后液固分离除去溶液中的氟。化学沉淀法常在高浓度含氟废水处理中采用,pH值一般为2左右,除氟效率一部分取决于固液分离效果,常用的沉淀剂为含钙化合物,如:生石灰、石灰乳等。
混凝沉淀法的工艺过程为:向待处理的废水中投加混凝剂,水中的氟化物被吸附于所形成的沉淀物中而共沉淀,然后把固体沉淀物分离出来,即可达到除氟的目的。混凝剂包含两类:絮凝剂和助凝剂。常见的絮凝剂分为两大类:铝盐和铁盐;常见的助凝剂是聚丙烯酰胺,助凝剂不能直接除氟,而是通过吸附架桥促进絮凝体的行成,提高沉降速度。
吸附法的工艺过程为:向含氟废水中加入多孔性固体相物质吸附其中的氟化物。废水中氟化物的吸附是一种与表面能有关的表面现象,它可分为靠吸附剂与吸附质之间的分子作用的物理吸附、靠化学键力作用的化学吸附及靠静电引力作用的离子交换吸附三种类型。常见的吸附剂有含铝类吸附剂、天然高分子吸附剂和稀土吸附剂等,吸附剂之所以具有良好的吸附性能,主要是因为它具有密集的细孔结构和巨大的比表面积,或具有能与吸附质分子形成稳定化学键的基团。含铝类吸附剂中常见的有活性氧化铝和分子筛。
含氟酸性废水成分复杂,其中除氢氟酸、氟硅酸、氟铁酸、氟钛酸及无机盐外,还含有大量的游离矿物酸,采用化学沉淀法、混凝沉淀法及吸附法处理,虽然能满足含氟废水达标排放的处理要求,但处理过程要消耗大量的碱来中和其中的酸,这不仅成倍增加了含氟废水的治理成本,而且导致氟及酸资源的严重浪费,产生的含氟废弃物极易造成二次污染。为此,人们也曾尝试过采用扩散渗析膜来分离含氟酸性废水中的氟与酸,但由于酸性废水中的氟主要以氢氟酸和络氟酸的形式存在,扩散渗析法不能将酸性废水中的氟与矿物酸有效分离,最后不得不仍然采用化学沉淀法或混凝沉淀法来处理含氟酸性废水。
发明内容
本发明的目的在于提供一种工艺简单,操作简便,环境友好的从含氟酸性废水中分离回收氟和酸的方法。
本发明一种从含氟酸性废水中分离回收氟和酸的方法,包括下述步骤:
步骤一:络氟
往含氟酸性废水中加入络氟剂,使溶液中的氟转化成络氟酸,过滤得络氟渣和含络氟酸的溶液;
步骤二:沉淀分离氟
往步骤一得到的含络氟酸的溶液中搅拌加入沉淀剂,使其中的络氟酸以络氟酸盐形式沉淀析出,过滤得络氟酸盐沉淀物和沉氟后液,所得络氟酸盐沉淀物直接作产品销售或用作氟化工产品的生产原料;
步骤三:沉氟后液综合利用
步骤二得到的沉氟后液直接作为酸溶液加以利用,或用阴离子扩散渗析膜脱除其中的盐后再加以利用,所得残液加碱中和回收其中的有价金属。
本发明一种从含氟酸性废水中分离回收氟和酸的方法中,所述的络氟是指按含氟酸性废水中的氟转化成络氟酸理论量的1~3倍加入络氟剂,室温搅拌0.5~15h,过滤得络氟渣和含络氟酸的溶液。
本发明一种从含氟酸性废水中分离回收氟和酸的方法中,所述的络氟剂选自二氧化硅、硅酸、硅酸钠,及在酸性溶液中可以溶解的含钛化合物或含铁化合物或含铝化合物或含锆化合物中的至少一种。
本发明一种从含氟酸性废水中分离回收氟和酸的方法中,所述在酸性溶液中可以溶解的含钛化合物是指氧化钛、偏钛酸、硫酸氧钛、氯化钛、硝酸钛中的至少一种;在酸性溶液中可以溶解的含铁化合物是指氧化铁、氢氧化铁、硫酸铁、氯化铁、硝酸铁中的至少一种;在酸性溶液中可以溶解的含铝化合物是指氧化铝、氢氧化铝、硫酸铝、氯化铝、硝酸铝中的至少一种;在酸性溶液中可以溶解的含锆化合物是指氧化锆、偏锆酸、硫酸氧锆、氯化锆、硝酸锆中的至少一种。
本发明一种从含氟酸性废水中分离回收氟和酸的方法中,所述的沉淀分离氟是指按步骤一得到溶液中的络氟酸转化成络氟酸盐沉淀理论量的1~5倍加入沉淀剂,-30℃~30℃搅拌2~20h,使其中的氟以络氟酸盐沉淀形式析出,过滤得络氟酸盐沉淀物和沉氟后液。
本发明一种从含氟酸性废水中分离回收氟和酸的方法中,所述的络氟酸沉淀剂选自氢氧化钠、硝酸钠、氯化钠、硫酸钠、硫酸氢钠、碳酸钠、碳酸氢钠、氢氧化钾、硝酸钾、氯化钾、硫酸钾、硫酸氢钾、碳酸钾、碳酸氢钾、氨水、氨气、硝酸铵、氯化铵、硫酸铵、硫酸氢铵、碳酸铵、碳酸氢铵、氧化钙、氢氧化钙、氯化钙、硝酸钙、硫酸钙、碳酸钙、碳酸氢钙、氧化钡、氢氧化钡、氯化钡、硝酸钡、碳酸钡、碳酸氢钡中的至少一种。
本发明一种从含氟酸性废水中分离回收氟和酸的方法中,沉氟后液用阴离子扩散渗析膜回收其中的酸,工艺参数为:控制料液流速为0.5~1.8L/h·m2、水与料液的流速比为0.5~1.5:1,回收得到酸,所得残液加碱中和至pH为5-11,沉淀析出其中的有价金属,过滤后加以回收。
从含氟酸性废水中分离回收氟的基本原理可用以下反应式来表示:
6F-+Mea++(6-a)H+=H(6-a)MeF6 (1)
H(6-a)MeF6+(6-a)A+=(6-a)H++A(6-a)MeF6↓ (2)
MeF6 (6-a)-+(6-a)/2Ae2+=Ae((6-a)/2)MeF6↓ (3)
其中Me=Si,Ti,Fe,Al,Zr;A+=K+,Na+,NH4 +;Ae=Ba,Ca。
本发明与已有的技术相比具有以下优点及效果:
本发明巧妙地利用氟与硅、钛、铁、铝等在酸性溶液中能与氟结合转化成络氟酸,络氟酸与钾离子、钠离子、铵根离子及钙离子等结合可形成络氟酸盐沉淀,从而可实现废水中的氟在强酸性条件下直接沉淀分离富集,过滤得到的沉氟后液通过阴离子扩散渗析膜处理后,不仅可回收利用其中的酸,还能进一步分离富集其中的有价金属,实现含氟酸性废水的资源化综合利用,具有工艺简单,操作简便,废水处理成本低,资源综合利用率高,环境友好等优点。
具体实施方式
下面结合实施例,对本发明作进一步描述,以下实施例旨在说明本发明而不是对本发明的进一步限定。
实施例1
取钽铌冶炼过程产生的矿萃残液1.5m3,按其中氟络合形成氟硅酸1.5倍加入石英粉,室温搅拌8h,过滤得络氟残渣和含氟硅酸的溶液。所得络氟残渣综合回收其中的有价金属,所得溶液按其中的氟硅酸-转化成氟硅酸钠沉淀理论量的1.3倍加入硫酸钠,室温搅拌2.5h,过滤得含氟硅酸钠的沉淀物和沉氟后液。所得含氟硅酸钠的沉淀物用作氟化工产品的生产原料,沉氟后液经扩散渗析膜处理处理得硫酸溶液和扩散渗析残液。所得硫酸溶液用作冶金化工的生产原料,扩散渗析残液经碱中和后中水回用。矿萃残液处理前后的实验结果如下:
实施例2
取钛材加工产生含硝酸-氢氟酸的洗涤废液2m3,按其中游离氢氟酸转化成氟钛酸理论量的1.5倍加入偏钛酸,室温搅拌0.5h,然后按溶液中的氟钛酸形成氟钛酸钙理论量的1.5倍加入氧化钙,-5℃搅拌5h,过滤得氟钛酸钙沉淀物和脱钛后液。所得氟钛酸钙直接作产品销售,脱钛后液补加适量氢氟酸后返回钛材加工洗涤工序继续使用。洗涤废液处理前后的实验结果如下:
HNO<sub>3</sub> | HF | ∑F | Ti | |
洗涤废液,g/L | 311.8 | 3.3 | 46.3 | 18.1 |
脱钛后液,g/L | 313.6 | --- | 0.5 | 0.06 |
Claims (4)
1.一种从含氟酸性废水中分离回收氟和酸的方法,包括下述步骤:
步骤一:络氟
往含氟酸性废水中加入络氟剂,使溶液中的氟转化成络氟酸,过滤得络氟渣和含络氟酸的溶液;按含氟酸性废水中的氟转化成络氟酸理论量的1.5~3倍加入络氟剂;所述的络氟剂选自在酸性溶液中可以溶解的含钛化合物或含锆化合物中的至少一种;
步骤二:沉淀分离氟
往步骤一得到的含络氟酸的溶液中搅拌加入沉淀剂,沉淀剂的加入量按步骤一得到溶液中的络氟酸转化成络氟酸盐沉淀理论量的1~5倍加入,-30℃~30℃搅拌2~20h,使其中的络氟酸以络氟酸盐形式沉淀析出,过滤得络氟酸盐沉淀物和沉氟后液,所得络氟酸盐沉淀物直接作产品销售或用作氟化工产品的生产原料; 沉淀剂选自氢氧化钠、硝酸钠、氯化钠、硫酸钠、硫酸氢钠、碳酸钠、碳酸氢钠、氢氧化钾、硝酸钾、氯化钾、硫酸钾、硫酸氢钾、碳酸钾、碳酸氢钾、氨水、氨气、硝酸铵、氯化铵、硫酸铵、硫酸氢铵、碳酸铵、碳酸氢铵、氧化钙、氢氧化钙、氯化钙、硝酸钙、硫酸钙、碳酸钙、碳酸氢钙、氧化钡、氢氧化钡、氯化钡、硝酸钡、碳酸钡、碳酸氢钡中的至少一种;
步骤三:沉氟后液综合利用
步骤二得到的沉氟后液直接作为酸溶液加以利用,或用阴离子扩散渗析膜脱除其中的盐后再加以利用,所得残液加碱中和回收其中的有价金属。
2.根据权利要求1所述的一种从含氟酸性废水中分离回收氟和酸的方法,其特征在于:所述的络氟是室温搅拌0.5~15h,过滤得络氟渣和含络氟酸的溶液。
3.根据权利要求1所述的一种从含氟酸性废水中分离回收氟和酸的方法,其特征在于:所述在酸性溶液中可以溶解的含钛化合物是指氧化钛、偏钛酸、硫酸氧钛、氯化钛、硝酸钛中的至少一种;在酸性溶液中可以溶解的含锆化合物是指氧化锆、偏锆酸、硫酸氧锆、氯化锆、硝酸锆中的至少一种。
4.根据权利要求1所述的一种从含氟酸性废水中分离回收氟和酸的方法,其特征在于:沉氟后液用阴离子扩散渗析膜回收其中的酸,工艺参数为:控制料液流速为0.5~1.8L/h·m2、水与料液的流速比为0.5~1.5:1,回收得到酸,所得残液加碱中和至pH为5-11,沉淀析出其中的有价金属,过滤后加以回收。
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CN104591462A (zh) * | 2015-01-15 | 2015-05-06 | 桂林电子科技大学 | 一种处理强酸性高氟废水的氟化物共沉淀法 |
CN105753211A (zh) * | 2016-03-24 | 2016-07-13 | 北京国环清华环境工程设计研究院有限公司 | 太阳能电池片或玻璃减薄生产废酸中氟回收方法与系统 |
CN105776221A (zh) * | 2016-04-01 | 2016-07-20 | 龚家竹 | 一种磷肥生产中氟资源回收的方法 |
CN106348328A (zh) * | 2016-10-25 | 2017-01-25 | 嘉善蓝欣涂料有限公司 | 一种利用含铝电抛液和含氟废水资源化回收酸液的方法 |
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