CN117247092A - Fluorine removing agent for fluorine-containing wastewater treatment and preparation method thereof - Google Patents
Fluorine removing agent for fluorine-containing wastewater treatment and preparation method thereof Download PDFInfo
- Publication number
- CN117247092A CN117247092A CN202311400712.8A CN202311400712A CN117247092A CN 117247092 A CN117247092 A CN 117247092A CN 202311400712 A CN202311400712 A CN 202311400712A CN 117247092 A CN117247092 A CN 117247092A
- Authority
- CN
- China
- Prior art keywords
- salt
- fluorine
- aluminum
- zirconium
- chloride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 124
- 239000011737 fluorine Substances 0.000 title claims abstract description 123
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 80
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229920001661 Chitosan Polymers 0.000 claims abstract description 44
- 239000000463 material Substances 0.000 claims abstract description 22
- 150000003754 zirconium Chemical class 0.000 claims abstract description 19
- 239000011368 organic material Substances 0.000 claims abstract description 17
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 17
- 150000003608 titanium Chemical class 0.000 claims abstract description 17
- 159000000003 magnesium salts Chemical class 0.000 claims abstract description 16
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 16
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 150000002505 iron Chemical class 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 26
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 26
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 26
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 26
- -1 alum Chemical compound 0.000 claims description 23
- 239000011259 mixed solution Substances 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- 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 description 15
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 15
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 13
- 235000011147 magnesium chloride Nutrition 0.000 claims description 13
- 239000004408 titanium dioxide Substances 0.000 claims description 13
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 229910021645 metal ion Inorganic materials 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-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
- 239000013522 chelant Substances 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 6
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- YTIVTFGABIZHHX-UHFFFAOYSA-N butynedioic acid Chemical compound OC(=O)C#CC(O)=O YTIVTFGABIZHHX-UHFFFAOYSA-N 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- HSBSUGYTMJWPAX-UHFFFAOYSA-N 2-hexenedioic acid Chemical compound OC(=O)CCC=CC(O)=O HSBSUGYTMJWPAX-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 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
- 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
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- 229960000250 adipic acid Drugs 0.000 claims description 2
- 229940037003 alum Drugs 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 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 claims description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 2
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 claims description 2
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 2
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 claims description 2
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims description 2
- 229940106681 chloroacetic acid Drugs 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 229960004887 ferric hydroxide Drugs 0.000 claims description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 2
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims description 2
- YXEUGTSPQFTXTR-UHFFFAOYSA-K lanthanum(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[La+3] YXEUGTSPQFTXTR-UHFFFAOYSA-K 0.000 claims description 2
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 2
- 239000011654 magnesium acetate Substances 0.000 claims description 2
- 235000011285 magnesium acetate Nutrition 0.000 claims description 2
- 229940069446 magnesium acetate Drugs 0.000 claims description 2
- 229960002337 magnesium chloride Drugs 0.000 claims description 2
- 229960005336 magnesium citrate Drugs 0.000 claims description 2
- 235000002538 magnesium citrate Nutrition 0.000 claims description 2
- 239000004337 magnesium citrate Substances 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 229960003390 magnesium sulfate Drugs 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 2
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 2
- 229910000348 titanium sulfate 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
- PLSARIKBYIPYPF-UHFFFAOYSA-H trimagnesium dicitrate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O PLSARIKBYIPYPF-UHFFFAOYSA-H 0.000 claims description 2
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims description 2
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 description 44
- 238000000034 method Methods 0.000 description 31
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 15
- 238000006115 defluorination reaction Methods 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 239000002699 waste material Substances 0.000 description 13
- 239000007788 liquid Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000001179 sorption measurement Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 6
- 230000006196 deacetylation Effects 0.000 description 6
- 238000003381 deacetylation reaction Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000010668 complexation reaction Methods 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 206010016818 Fluorosis Diseases 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 208000004042 dental fluorosis Diseases 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002516 radical scavenger Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- 238000004334 fluoridation Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000004411 aluminium Substances 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
- 230000008901 benefit Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000001684 chronic effect Effects 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000012629 purifying agent Substances 0.000 description 1
- 238000012113 quantitative test Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 210000001519 tissue Anatomy 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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- 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
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
Abstract
The invention discloses a fluorine removing agent for fluorine-containing wastewater treatment and a preparation method thereof, wherein the fluorine removing agent is prepared by taking chitosan as a biological molecular framework, and taking magnesium salt, titanium salt, zirconium salt, aluminum salt, ferric salt, rare earth materials and organic materials as blending raw materials; wherein, magnesium salt: titanium salt: zirconium salt: aluminum salt: iron salt: rare earth material: organic material: the mass ratio of the chitosan is as follows: 1-30: 1-30: 2-20: 2-10: 2-10: 20-50: 2-10: 1-10. The invention is based on the existing compound defluorinating agent, and magnesium salt, titanium salt, zirconium salt and organic material are additionally added to prepare the novel defluorinating agent, which has the characteristics of good stability, wide application range and being beneficial to large-scale application.
Description
Technical Field
The invention relates to the technical field of water treatment agents, in particular to a fluorine removal agent for fluorine-containing wastewater treatment and a preparation method thereof.
Background
In the production of fluoridation industries such as fluoridation ore exploitation, aluminium electrolysis, photovoltaics, electroplating, semiconductors, glass, fertilizers, etc., a large amount of "three wastes" containing fluorine, including wastewater containing fluorine ions, are generated, so that fluorine enters the environment and is extremely easy to cause fluorine pollution if being poorly managed. If the human body ingests excessive fluorine for a long time, the chronic fluorosis is easily caused, hard tissues such as bones and teeth are easily damaged, and in severe cases, fluorosis and fluorosis teeth can appear, and even the risk of cancer is increased. And it is proved by researches that excessive fluorine intake has an influence on the intelligence quotient of children. Thus, the pollutant emission standard of urban sewage treatment plants (GB 18918-2002) prescribes that the upper limit of the fluoride emission standard is 1.5mg/L, and the fluorine content in the fluorine-containing wastewater and the discharged water is clearly defined.
The treatment process of fluoride in wastewater at home and abroad mainly comprises a precipitation method (chemical precipitation method and coagulating precipitation method), an adsorption method, an electric flocculation method, an electrodialysis method, a reverse osmosis method, an ion exchange method and the like. When fluorine-containing wastewater is treated, a fluorine removing agent is generally adopted to perform fluorine removal based on chemical reaction with fluorine ions in water, and precipitation is generated through adsorption, complexation and flocculation, so that the preparation of the fluorine removing agent is common in production. The existing preparation method of the fluorine-removing agent for fluorine-containing wastewater treatment is mainly used for preparing single-type purifying agents, the fluorine-removing effect is poor, the fluorine-removing agent is poor in performance and large in dosage, the treatment cost of fluorine-containing wastewater is increased, and the economic benefit is low.
CN114988547a discloses a compound defluorinating agent, which is prepared from the following components in mass ratio, chitosan is taken as a molecular skeleton, and an aluminum-iron-rare earth metal blend is loaded on the skeleton to form a chelate with a plurality of active sites; wherein, aluminum salt: iron salt: rare earth material: chitosan: the mass ratio of the acetic acid is 5-10: 5-10: 15-20: 5-10: 3 to 5. The fluorine removing agent takes chitosan as a framework, and is fully chelated with metal ion coprecipitates in acetic acid, so that the mechanical strength of the chitosan under an acidic condition is effectively improved, and meanwhile, secondary pollution caused by metal ion counter-dissolution can be effectively avoided; in addition, the coprecipitate formed by a plurality of metal ions can not only increase the applicable pH range of the fluorine removing agent, but also greatly improve the adsorption removal performance of fluorine ions and the sedimentation speed of sludge flocs. The preparation method obtains a plurality of metal ion coprecipitates by a reverse coprecipitation method, and the coprecipitates have uniform particle size and no agglomeration phenomenon, so that metal active sites on chitosan are dispersedUniform and improved adsorption performance of the defluorinating agent. The defluorination agent is used for defluorination, the defluorination efficiency is high, the removal rate of fluorine ions reaches more than 95%, and F - The concentration is reduced to below 1.0 mg/L. However, the fluorine removal agent prepared by the method has serious liquid-solid layering phenomenon after the storage period time of the product is prolonged, and the fluorine removal test is carried out at intervals of a certain period of time, so that the fluorine removal rate of the product is greatly lower than that of the product when the preparation is just finished, and the stability is poor; the defluorinating agent is suitable for treating industrial wastewater with low concentration, small water quantity, high water inlet requirement and low discharge requirement, and has a narrow application range; the product can raise the original turbidity of the wastewater solution while carrying out defluorination treatment on the wastewater, and the COD of the wastewater is not lowered and reversely raised although the fluorine content of the wastewater after treatment can be reduced to below 1mg/L, and the pH change of the wastewater after treatment by the defluorination agent product is larger, so that the wastewater is required to be subjected to subsequent alkali addition adjustment, the original water treatment flow is required to be changed, and the wastewater is unfavorable for large-scale application.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a fluorine-removing agent for fluorine-containing wastewater treatment, which solves the technical problems that the existing fluorine-removing agent has poor product stability and narrow action range and is not beneficial to large-scale application.
Further, a preparation method of the fluorine removing agent is provided.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the fluorine removing agent for fluorine-containing wastewater treatment is prepared by taking chitosan as a biological molecular framework, and taking magnesium salt, titanium salt, zirconium salt, aluminum salt, ferric salt, rare earth materials and organic materials as blending raw materials;
wherein, magnesium salt: titanium salt: zirconium salt: aluminum salt: iron salt: rare earth material: organic material: the mass ratio of the chitosan is as follows: 1-30: 1-30: 2-20: 2-10: 2-10: 20-50: 2-10: 1 to 10.
Further, magnesium salt: titanium salt: zirconium salt: aluminum salt: iron salt: rare earth material: organic material: the mass ratio of the chitosan is as follows: 3 to 6:3 to 6:3 to 6: 5-10: 5-10: 20-30: 2 to 5:3 to 5.
Further, the magnesium salt comprises at least one of magnesium chloride, magnesium sulfate, magnesium citrate and magnesium acetate; the titanium salt comprises at least one of titanium dioxide, titanium tetrachloride, titanium sulfate and titanyl sulfate; the zirconium salt comprises at least one of zirconium dioxide, zirconium chloride, zirconium silicate and zirconium sulfate; the aluminum salt comprises at least one of aluminum chloride, aluminum sulfate, alum, aluminum oxide, aluminum hydroxide, calcium aluminate, sodium aluminate and polyaluminum chloride; the ferric salt comprises at least one of ferric sulfate, ferric chloride, aluminum ferric chloride, ferric oxide, ferric hydroxide and polymeric aluminum ferric sulfate; the rare earth material is any one of lanthanum nitrate, lanthanum chloride, lanthanum oxide, lanthanum hydroxide, cerium nitrate, cerium chloride, cerium oxide or cerium hydroxide; the organic material is any one of oxalic acid, tartaric acid, citric acid, naphthalene dicarboxylic acid, 1, 4-butane dicarboxylic acid, 1, 4-butene dicarboxylic acid, acetylene dicarboxylic acid, phthalic acid, 1, 2-phthalic acid, 1, 3-phthalic acid, acetylene dicarboxylic acid, acetic acid, ethyl acetate or chloroacetic acid.
The invention also provides a preparation method of the fluorine removal agent for fluorine-containing wastewater treatment, which comprises the following steps:
(1) Adding magnesium salt, titanium salt, zirconium salt, aluminum salt, ferric salt, rare earth material and organic material into water according to the mass ratio of claim 1 or 2, fully dissolving, and uniformly stirring at room temperature to obtain a mixed solution;
(2) Slowly dripping the mixed solution into a sodium hydroxide solution to react to generate a metal ion coprecipitate;
(3) Adding the mixture prepared in the step (2) into chitosan solution, fully dissolving and uniformly stirring to fully chelate inorganic metal ions with chitosan to obtain mixed solution;
(4) And drying the mixed solution, taking out, cooling to room temperature, and crushing and grinding to obtain the powdery fluorine removing agent.
And (3) stirring in the step (1) for 3-10 hours.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention is based on the existing compound defluorinating agent, and magnesium salt, titanium salt, zirconium salt and organic material are additionally added to prepare the novel defluorinating agent, and the technical problems that the existing defluorinating agent is poor in product stability, narrow in application range and unfavorable for large-scale application are solved through compatibility and synergistic effect of components. A large number of stability practices prove that the defluorinating agent has good stability, the removal rate of 95% or more is still maintained after the time interval is increased, and the pH value of the treated wastewater does not change greatly; therefore, the consumption of acid and alkali for neutralizing the wastewater is reduced, the engineering application cost can be reduced, and the method is suitable for large-scale application.
Wherein, the fluorine removing agent has higher zero potential point by adding a plurality of inorganic metal ions, the pH range suitable for action is widened, and higher fluorine removing rate can be maintained within 3-11. The magnesium salt is added, so that the internal structure of the fluorine removing agent is tighter, the specific surface area is obviously increased, active sites combined with fluorine ions are increased, and the active sites are more stable, thereby improving the adsorption efficiency of the fluorine ions. On the one hand, the titanium salt is added, the specific surface area of the material can be increased through loading, and the adsorption active site is increased; on the other hand, the supported titanium salt can increase the fluorine removal efficiency, and the application range of adjusting the pH is correspondingly widened, and the adsorption capacity of fluorine can be enhanced by adding the titanium ion due to the stronger binding force between the titanium ion and the fluorine ion. The zirconium salt is added to remove fluorine ions in the wastewater through ion exchange, zr-F bonds are formed in the solution after the zirconium salt is added, and the fluorine ion removal process not only has ion exchange but also has complexation reaction, the reaction energy of the complexation reaction is larger than that of the ion exchange, and the complexation reaction can strengthen the selective adsorption of the fluorine removing agent on the fluorine ions; meanwhile, zirconium salt can react with fluoride ions to generate precipitate, and compared with other anions and fluoride ions, the stability of the fluoride removing agent after adding the zirconium salt is higher, and the capability of resisting the interference of coexisting anions is greatly enhanced. The organic material is added to enable various metals to be more tightly compounded with chitosan, so that the stability of the product is obviously enhanced, and the fluorine removal efficiency is greatly improved; after the organic material is added, the dissolution of fine inorganic metal ions can be promoted, and insoluble metal solids are mutually bonded into a larger shapeThe compound in the shape further undergoes polymerization reaction, and the organic material is added to carry out doping modification at the same time, so that the fluorine removal capability of the fluorine removal agent is improved, the fluorine removal agent liquid product is kept stable, free inorganic metal ions are not contained, the fluorine removal agent is high in purity and low in impurity content, and the fluorine removal agent is favorable for drying and roasting to obtain a solid sample and is convenient to store and use. Therefore, the fluorine removing agent prepared by the invention is more environment-friendly, does not affect the water body, and does not increase pollutants such as COD, N, P and the like in the water body; is more efficient in removing fluorine and has high emission standard for fluoride ions (F - Less than 1 mg/L), only one reaction precipitation is needed in the industry and the region; the preparation is more stable, various metal ions and organic functional groups are grafted, the yielding water is more stable, the removal rate is higher, and fluoride ions are not dissolved out due to analysis along with the fluctuation of pH within the range of pH of 3-11. The wastewater treated by the defluorinating agent can reduce the salinity and the conductivity, is suitable for industrial wastewater in coal chemical industry, photovoltaics, conductors, electronics, glass and the like, and has wide application range.
2. The defluorination agent has wide application range, can remove fluorine from the fluorine-containing wastewater with the fluoride ion concentration of 10-30 mg/L, has high defluorination efficiency, and has the fluoride ion removal rate of more than 99 percent for the fluorine-containing wastewater with the initial fluoride ion concentration of 30 mg/L.
3. According to the preparation method of the fluorine-removing agent for fluorine-containing wastewater treatment, the mixed solution is dried, the water molecules are removed through calcination and the mixed metal salt particles are refined and micronized to obtain the raw materials with small particle sizes, so that the problems of agglomeration and aggregation of magnesium salt, titanium salt, zirconium salt, aluminum salt, ferric salt and rare earth materials (lanthanum and cerium) in the mixing process are avoided, the subsequent dissolution quality is improved, the components in the fluorine-removing agent are uniformly mixed, the specific surface area of the fluorine-removing agent is increased, and the fluorine-removing performance of the fluorine-removing agent is improved. The chitosan has double helix three-dimensional structure, wide sources, low cost and easy obtainment, large specific surface area, a large number of functional groups and biodegradability, so that the prepared defluorinating agent has good defluorinating performance and excellent purifying effect,
has wide applicability and is an environment-friendly material.
Detailed Description
The following describes the embodiments of the present invention in further detail with reference to specific examples.
Numerical ranges in this disclosure are understood to also specifically disclose each intermediate value between the upper and lower limits of the ranges. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control. As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The experimental methods used in the present invention are conventional methods unless otherwise specified.
The materials, reagents and the like used in the present invention can be synthesized by a method of purchase or known method unless otherwise specified.
In the quantitative test of the invention, three repeated experiments are set, and the results are averaged.
Example 1
The embodiment provides a fluorine removing agent for fluorine-containing wastewater treatment, which is prepared by taking chitosan as a biological molecular framework and magnesium chloride, titanium dioxide, zirconium chloride, aluminum chloride, polymeric ferric sulfate, lanthanum nitrate and phthalic acid as blending raw materials;
wherein, magnesium chloride: titanium dioxide: zirconium chloride: aluminum chloride: polymeric ferric sulfate: lanthanum nitrate: phthalic acid: the mass ratio of the chitosan is as follows: 3:3:3:5:5:20:10:5. the degree of deacetylation of chitosan was 95%.
The fluorine removing agent is prepared by the following method and specifically comprises the following steps:
(1) 3 parts of magnesium chloride, 3 parts of titanium dioxide, 3 parts of zirconium chloride, 5 parts of aluminum chloride, 5 parts of polymeric ferric sulfate, 20 parts of lanthanum nitrate and 1 part of phthalic acid are mixed and added into deionized water, and the mixture is fully stirred for 4 hours at 25 ℃ to obtain a mixed solution A;
(2) Slowly dripping the mixed solution A into NaOH solution with the mass concentration of 10%; reacting to generate a metal coprecipitate;
(3) Dissolving 5 parts of chitosan in deionized water, wherein the deacetylation degree of the chitosan is 95%, adding the solution mixture obtained in the step (2) into the chitosan solution, and fully stirring for 12 hours to fully chelate the metal coprecipitate and the chitosan to obtain a mixed solution B;
(4) And (3) placing the mixed solution B in an oven, drying at 80 ℃, taking out, cooling to room temperature, and crushing and grinding to obtain the powdery fluorine removing agent.
Example 2
The embodiment provides a fluorine removing agent for fluorine-containing wastewater treatment, which is prepared by taking chitosan as a biological molecular framework and magnesium chloride, titanium dioxide, zirconium chloride, aluminum chloride, polymeric ferric sulfate, lanthanum chloride and phthalic acid as blending raw materials;
wherein, magnesium chloride: titanium dioxide: zirconium chloride: aluminum chloride: polymeric ferric sulfate: lanthanum chloride: phthalic acid: the mass ratio of the chitosan is as follows: 6:3:3:10:5:30:2:3. the degree of deacetylation of chitosan was 95%.
The fluorine removing agent is prepared by the following method and specifically comprises the following steps:
(1) Mixing 6 parts of magnesium chloride, 3 parts of titanium dioxide, 3 parts of zirconium chloride, 10 parts of aluminum chloride, 5 parts of polymeric ferric sulfate, 20 parts of lanthanum chloride and 2 parts of phthalic acid, adding the mixture into deionized water, and fully stirring the mixture at 25 ℃ for 6 hours to obtain a mixed solution A;
(2) Slowly dripping the mixed solution A into NaOH solution with the mass concentration of 10%; reacting to generate a metal coprecipitate;
(3) Dissolving 3 parts of chitosan in deionized water, wherein the deacetylation degree of the chitosan is 95%, adding the solution mixture obtained in the step (2) into the chitosan solution, and fully stirring for 12 hours to fully chelate the metal coprecipitate and the chitosan to obtain a mixed solution B;
(4) And (3) placing the mixed solution B in an oven, drying at 80 ℃, taking out, cooling to room temperature, and crushing and grinding to obtain the powdery fluorine removing agent.
Example 3
The embodiment provides a fluorine removing agent for fluorine-containing wastewater treatment, which is prepared by taking chitosan as a biological molecular framework and taking magnesium chloride, titanium dioxide, zirconium chloride, aluminum chloride, polymeric ferric sulfate, cerium nitrate and phthalic acid as blending raw materials;
wherein, magnesium chloride: titanium dioxide: zirconium chloride: aluminum chloride: polymeric ferric sulfate: cerium nitrate: phthalic acid: the mass ratio of the chitosan is as follows: 6:3:6:10:10:20:5:5. the degree of deacetylation of chitosan was 95%.
The fluorine removing agent is prepared by the following method and specifically comprises the following steps:
(1) Mixing 6 parts of magnesium chloride, 3 parts of titanium dioxide, 6 parts of zirconium chloride, 10 parts of aluminum chloride, 10 parts of polymeric ferric sulfate, 20 parts of cerium nitrate and 1 part of phthalic acid, adding the mixture into deionized water, and fully stirring the mixture at 25 ℃ for 6 hours to obtain a mixed solution A;
(2) Slowly dripping the mixed solution A into NaOH solution with the mass concentration of 10%; reacting to generate a metal coprecipitate;
(3) Dissolving 5 parts of chitosan in deionized water, wherein the deacetylation degree of the chitosan is 95%, adding the solution mixture obtained in the step (2) into the chitosan solution, and fully stirring for 12 hours to fully chelate the metal coprecipitate and the chitosan to obtain a mixed solution B;
(4) And (3) placing the mixed solution B in an oven, drying at 80 ℃, taking out, cooling to room temperature, and crushing and grinding to obtain the powdery fluorine removing agent.
Comparative example 1
Comparative example 1 provides a fluorine scavenger, which is prepared by the same process as in example 1, except that: magnesium chloride: titanium dioxide: zirconium chloride: aluminum chloride: polymeric ferric sulfate: lanthanum nitrate: phthalic acid: the mass ratio of the chitosan is as follows: 3:3:3:5:5:12:10:5.
comparative example 2
Comparative example 2 provides a fluorine scavenger, which is prepared by the same process as in example 2, except that: magnesium chloride: titanium dioxide: zirconium chloride: aluminum chloride: polymeric ferric sulfate: lanthanum chloride: phthalic acid: the mass ratio of the chitosan is as follows: 6:3:3:10:5:30:1:3.
comparative example 3
Comparative example 3 provides a fluorine scavenger, which is prepared by the same process as in example 3, except that: and (3) directly placing the mixed solution obtained in the step (2) in an oven after the metal coprecipitate is generated in the step (2) without chitosan, drying at 70 ℃, and grinding to obtain the powdery fluorine removing agent.
Application examples and comparative examples of the defluorinating agent of the present invention
1. The method for removing fluorine by adopting the fluorine removing agent obtained in the embodiment 1 specifically comprises the following steps:
(1) Detecting the concentration of fluoride ions in the fluoride-containing waste liquid to be 30mg/L, and controlling the pH value of the waste water to be 3-7;
(2) Adding a fluorine removing agent into the fluorine-containing waste liquid until the concentration is 600mg/L, and stirring for 3 hours;
(3) Adding NaOH with the mass concentration of 10% and HCl with the mass concentration of 10% into the reacted wastewater, and regulating the pH value of the wastewater in a tank to be 7.0-9.0;
(4) F in wastewater after defluorination - The content is less than 1mg/L, and can reach the emission standard.
2. The method for removing fluorine by adopting the fluorine removing agent obtained in the embodiment 2 specifically comprises the following steps:
(1) Detecting the concentration of fluoride ions in the fluoride-containing waste liquid to be 10mg/L, and controlling the pH value of the waste water to be 3-7;
(2) Adding a fluorine removing agent into the fluorine-containing waste liquid until the concentration is 800mg/L, and stirring for 3 hours;
(3) Adding NaOH with the mass concentration of 10% and HCl with the mass concentration of 10% into the reacted wastewater, and regulating the pH value of the wastewater in a tank to be 7.0-9.0;
(4) F in wastewater after defluorination - The content is less than 1mg/L, and can reach the emission standard.
3. The method for removing fluorine by adopting the fluorine removing agent obtained in the embodiment 3 specifically comprises the following steps:
(1) Detecting the concentration of fluoride ions in the fluoride-containing waste liquid to be 20mg/L, and controlling the pH value of the waste water to be 3-7;
(2) Adding a fluorine removing agent into the fluorine-containing waste liquid until the concentration is 1000mg/L, and stirring for 3 hours;
(3) Adding NaOH with the mass concentration of 10% and HCl with the mass concentration of 10% into the reacted wastewater, and regulating the pH value of the wastewater in a tank to be 7.0-9.0;
(4) F in wastewater after defluorination - The content is less than 1mg/L, and can reach the emission standard.
4. The method for removing fluorine by adopting the fluorine removing agent obtained in the comparative example 1 specifically comprises the following steps:
(1) Detecting the concentration of fluoride ions in the fluoride-containing waste liquid to be 30mg/L, and controlling the pH value of the waste water to be 3-7;
(2) Adding a fluorine removing agent into the fluorine-containing waste liquid until the concentration is 600mg/L, and stirring for 3 hours;
(3) Adding NaOH with the mass concentration of 10% and HCl with the mass concentration of 10% into the reacted wastewater, and regulating the pH value of the wastewater in a tank to be 7.0-9.0;
(4) F in wastewater after defluorination - The content is 8-12 mg/L, which is higher than the emission standard.
This is because, according to analysis, the rare earth material is added in a smaller proportion than in example 1, resulting in the rare earth material to F - Is caused by the reduction of the adsorption amount.
5. The method for removing fluorine by adopting the fluorine removing agent obtained in the comparative example 2 specifically comprises the following steps:
(1) Detecting the concentration of fluoride ions in the fluoride-containing waste liquid to be 10mg/L, and controlling the pH value of the waste water to be 3-7;
(2) Adding a fluorine removing agent into the fluorine-containing waste liquid until the concentration is 800mg/L, and stirring for 3 hours;
(3) Adding NaOH with the mass concentration of 10% and HCl with the mass concentration of 10% into the reacted wastewater, and regulating the pH value of the wastewater in a tank to be 7.0-9.0;
(4) F in wastewater after defluorination - The content is 3-5 mg/L, which is higher than the emission standard.
This is because, according to analysis, the addition ratio of the organic matter is smaller than that of example 2, and thus the polymerization and co-precipitation of the metal copolymer are not complete, and the removal performance of the fluorine ions is lowered.
6. The method for removing fluorine by adopting the fluorine removing agent obtained in the comparative example 3 specifically comprises the following steps:
(1) Detecting the concentration of fluoride ions in the fluoride-containing waste liquid to be 20mg/L, and controlling the pH value of the waste water to be 3-7;
(2) Adding a fluorine removing agent into the fluorine-containing waste liquid until the concentration is 1000mg/L, and stirring for 3 hours;
(3) Adding NaOH with the mass concentration of 10% and HCl with the mass concentration of 10% into the reacted wastewater, and regulating the pH value of the wastewater in a tank to be 7.0-9.0;
(4) F in wastewater after defluorination - The content is 10-12 mg/L, which is higher than the emission standard.
This is analyzed because, compared with example 3, comparative example 3 does not have a skeleton in which chitosan is a metal co-precipitate, resulting in a lack of skeleton support, and also lack of adsorptivity for fluoride ions, and a decrease in fluoride ion removal performance.
7. The treatment effect of the fluorine-containing wastewater of a certain semiconductor enterprise after adding the fluorine removing agent is shown in table 1.
TABLE 1 comparison of the defluorination effect of defluorination agent on semiconductor fluorine-containing wastewater
As is clear from Table 1, the fluorine removal by using the fluorine removing agent of the present invention can stabilize the fluorine removal rate at 95% or more, and the fluorine removal efficiency is high and the fluorine removal effect is stable. The fluorine removal efficiency is far higher than that of the fluorine removal agent and the activated alumina.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the technical solution, and those skilled in the art should understand that modifications and equivalents may be made to the technical solution of the present invention without departing from the spirit and scope of the present invention, and all such modifications and equivalents are included in the scope of the claims.
Claims (5)
1. The fluorine removing agent for fluorine-containing wastewater treatment is characterized in that chitosan is used as a biological molecular framework, and magnesium salt, titanium salt, zirconium salt, aluminum salt, ferric salt, rare earth material and organic material are used as blending raw materials to prepare the fluorine removing agent;
wherein, magnesium salt: titanium salt: zirconium salt: aluminum salt: iron salt: rare earth material: organic material: the mass ratio of the chitosan is as follows: 1-30: 1-30: 2-20: 2-10: 2-10: 20-50: 2-10: 1-10.
2. The fluorine removal agent for fluorine-containing wastewater treatment according to claim 1, wherein the magnesium salt: titanium salt: zirconium salt: aluminum salt: iron salt: rare earth material: organic material: the mass ratio of the chitosan is as follows: 3 to 6:3 to 6:3 to 6: 5-10: 5-10: 20-30: 2 to 5: 3-5.
3. The fluorine removal agent for fluorine-containing wastewater treatment according to claim 1, wherein the magnesium salt comprises at least one of magnesium chloride, magnesium sulfate, magnesium citrate, and magnesium acetate; the titanium salt comprises at least one of titanium dioxide, titanium tetrachloride, titanium sulfate and titanyl sulfate; the zirconium salt comprises at least one of zirconium dioxide, zirconium chloride, zirconium silicate and zirconium sulfate; the aluminum salt comprises at least one of aluminum chloride, aluminum sulfate, alum, aluminum oxide, aluminum hydroxide, calcium aluminate, sodium aluminate and polyaluminum chloride; the ferric salt comprises at least one of ferric sulfate, ferric chloride, aluminum ferric chloride, ferric oxide, ferric hydroxide and polymeric aluminum ferric sulfate; the rare earth material is any one of lanthanum nitrate, lanthanum chloride, lanthanum oxide, lanthanum hydroxide, cerium nitrate, cerium chloride, cerium oxide or cerium hydroxide; the organic material is any one of oxalic acid, tartaric acid, citric acid, naphthalene dicarboxylic acid, 1, 4-butane dicarboxylic acid, 1, 4-butene dicarboxylic acid, acetylene dicarboxylic acid, phthalic acid, 1, 2-phthalic acid, 1, 3-phthalic acid, acetylene dicarboxylic acid, acetic acid, ethyl acetate or chloroacetic acid.
4. The preparation method of the fluorine removal agent for fluorine-containing wastewater treatment is characterized by comprising the following steps:
(1) Adding magnesium salt, titanium salt, zirconium salt, aluminum salt, ferric salt, rare earth material and organic material into water according to the mass ratio of claim 1 or 2, fully dissolving, and uniformly stirring at room temperature to obtain a mixed solution;
(2) Slowly dripping the mixed solution into a sodium hydroxide solution to react to generate a metal ion coprecipitate;
(3) Adding the mixture prepared in the step (2) into chitosan solution, fully dissolving and uniformly stirring to fully chelate inorganic metal ions with chitosan to obtain mixed solution;
(4) And drying the mixed solution, taking out, cooling to room temperature, and crushing and grinding to obtain the powdery fluorine removing agent.
5. The method for producing a fluorine-removing agent for use in fluorine-containing wastewater treatment according to claim 4, wherein the stirring in the step (1) is carried out for 3 to 10 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311400712.8A CN117247092A (en) | 2023-10-26 | 2023-10-26 | Fluorine removing agent for fluorine-containing wastewater treatment and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311400712.8A CN117247092A (en) | 2023-10-26 | 2023-10-26 | Fluorine removing agent for fluorine-containing wastewater treatment and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117247092A true CN117247092A (en) | 2023-12-19 |
Family
ID=89126459
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311400712.8A Pending CN117247092A (en) | 2023-10-26 | 2023-10-26 | Fluorine removing agent for fluorine-containing wastewater treatment and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117247092A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117563685A (en) * | 2024-01-16 | 2024-02-20 | 山东晶源环保科技有限公司 | Efficient wastewater defluorinating agent and preparation and use methods thereof |
-
2023
- 2023-10-26 CN CN202311400712.8A patent/CN117247092A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117563685A (en) * | 2024-01-16 | 2024-02-20 | 山东晶源环保科技有限公司 | Efficient wastewater defluorinating agent and preparation and use methods thereof |
| CN117563685B (en) * | 2024-01-16 | 2024-04-02 | 山东晶源环保科技有限公司 | Efficient wastewater defluorinating agent and preparation and use methods thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100542976C (en) | Method with flyash and kaolin production compound aluminium silicate polymer ferric flocculant | |
| CN104556331B (en) | PAC (polyaluminium chloride)-modified sodium alginate inorganic-organic composite flocculant and preparation method thereof | |
| CN117247092A (en) | Fluorine removing agent for fluorine-containing wastewater treatment and preparation method thereof | |
| CN105036269B (en) | A kind of multiple-effect water treatment agent and preparation method thereof and method for treating water | |
| CN110040878A (en) | A kind of fluoride waste deep treatment method | |
| CN112850867B (en) | Deep defluorination medicament and preparation method thereof | |
| Ye et al. | Chemical precipitation granular sludge (CPGS) formation for copper removal from wastewater | |
| CN108975420A (en) | COD (COD) removes mixture of powders | |
| CN1385373A (en) | Coagulant for sewage treatment | |
| CN110304703B (en) | Preparation method for producing polyaluminium chloride water purifying agent by using aluminium ash | |
| CN113860458B (en) | Composite chelating agent and preparation method and application thereof | |
| CN101492192A (en) | Coagulating agent for treating wastewater containing fluorine and use process thereof | |
| CN104973668A (en) | Preparation method of organically modified polymeric ferric sulfate water purification agent | |
| CN103964554B (en) | Polyaluminum sulfate titanium-polydimethyldiallylachloride chloride composite coagulant and preparation and application method thereof | |
| CN1762848A (en) | Coagulant for disposing dying waste water and its production method | |
| CN101745362B (en) | Water defluorination agent preparation method and application | |
| CN110745926A (en) | Preparation method of coagulant for removing phosphorus in water body | |
| CN107487952B (en) | Combined treatment method for beneficiation wastewater containing xanthate residues | |
| CN102206001A (en) | Composite decolorizer as well as preparation method and application thereof | |
| CN109019805A (en) | A kind of organically-modified polysilicate aluminium ferric flocculant and preparation method | |
| CN107162143A (en) | Dyeing waste water purifies flocculant and its dyeing waste water purification applications | |
| CN1460648A (en) | Double-machine flocculant | |
| CN112479328A (en) | Preparation method of magnetic polyaluminum ferric silicate flocculant | |
| CN111302409A (en) | Sewage phosphorus removal agent, preparation method and application thereof | |
| CN110104744B (en) | Magnetic flocculant using steel mill red dust as material and application and use method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |