CN110451704A - A kind of processing method of fluorine-containing recycle-water - Google Patents
A kind of processing method of fluorine-containing recycle-water Download PDFInfo
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- CN110451704A CN110451704A CN201910815633.0A CN201910815633A CN110451704A CN 110451704 A CN110451704 A CN 110451704A CN 201910815633 A CN201910815633 A CN 201910815633A CN 110451704 A CN110451704 A CN 110451704A
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- Prior art keywords
- water
- fluorine
- edi
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 141
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 70
- 239000011737 fluorine Substances 0.000 title claims abstract description 70
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 238000003672 processing method Methods 0.000 title claims abstract description 24
- 239000002351 wastewater Substances 0.000 claims abstract description 85
- 238000000034 method Methods 0.000 claims abstract description 66
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 35
- 239000012498 ultrapure water Substances 0.000 claims abstract description 35
- 230000015556 catabolic process Effects 0.000 claims abstract description 28
- 238000006731 degradation reaction Methods 0.000 claims abstract description 28
- 230000008569 process Effects 0.000 claims abstract description 25
- 238000004659 sterilization and disinfection Methods 0.000 claims abstract description 20
- 238000004062 sedimentation Methods 0.000 claims abstract description 16
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 15
- 238000005189 flocculation Methods 0.000 claims abstract description 14
- 230000016615 flocculation Effects 0.000 claims abstract description 14
- 230000001954 sterilising effect Effects 0.000 claims abstract description 14
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 60
- 238000012545 processing Methods 0.000 claims description 39
- 229920005989 resin Polymers 0.000 claims description 26
- 239000011347 resin Substances 0.000 claims description 26
- 238000004519 manufacturing process Methods 0.000 claims description 22
- 239000002699 waste material Substances 0.000 claims description 22
- 239000012528 membrane Substances 0.000 claims description 21
- 150000002500 ions Chemical class 0.000 claims description 17
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 17
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 17
- 239000004794 expanded polystyrene Substances 0.000 claims description 13
- 229920005990 polystyrene resin Polymers 0.000 claims description 13
- 238000009296 electrodeionization Methods 0.000 claims description 12
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 11
- 239000000920 calcium hydroxide Substances 0.000 claims description 11
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 11
- 239000000701 coagulant Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 239000006228 supernatant Substances 0.000 claims description 7
- 239000001110 calcium chloride Substances 0.000 claims description 6
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 6
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 230000005611 electricity Effects 0.000 claims description 4
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000005374 membrane filtration Methods 0.000 abstract description 2
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 16
- 230000000694 effects Effects 0.000 description 15
- 238000005516 engineering process Methods 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 10
- -1 hydroxyl radical free radical Chemical class 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 8
- 239000011575 calcium Substances 0.000 description 8
- 229910052791 calcium Inorganic materials 0.000 description 8
- 238000006115 defluorination reaction Methods 0.000 description 8
- 230000008929 regeneration Effects 0.000 description 8
- 238000011069 regeneration method Methods 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 7
- 239000003463 adsorbent Substances 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
- 229910052749 magnesium Inorganic materials 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 230000001376 precipitating effect Effects 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 6
- 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 6
- 229910002651 NO3 Inorganic materials 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000009388 chemical precipitation Methods 0.000 description 6
- 238000000909 electrodialysis Methods 0.000 description 6
- 238000012544 monitoring process Methods 0.000 description 6
- 238000005498 polishing Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 5
- KIZFHUJKFSNWKO-UHFFFAOYSA-M calcium monohydroxide Chemical compound [Ca]O KIZFHUJKFSNWKO-UHFFFAOYSA-M 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000003456 ion exchange resin Substances 0.000 description 5
- 229920003303 ion-exchange polymer Polymers 0.000 description 5
- 238000004377 microelectronic Methods 0.000 description 5
- 239000005416 organic matter Substances 0.000 description 5
- 238000010525 oxidative degradation reaction Methods 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 230000002708 enhancing effect Effects 0.000 description 4
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000004065 wastewater treatment Methods 0.000 description 4
- 230000033228 biological regulation Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000010440 gypsum Substances 0.000 description 3
- 229910052602 gypsum Inorganic materials 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 238000000108 ultra-filtration Methods 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 230000004308 accommodation Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 239000010457 zeolite Substances 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
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 238000006087 Brown hydroboration reaction Methods 0.000 description 1
- QDHHCQZDFGDHMP-UHFFFAOYSA-N Chloramine Chemical class ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 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
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000007646 directional migration Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005685 electric field effect Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004334 fluoridation Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 238000001039 wet etching Methods 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
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
-
- 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
- C02F1/52—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
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
Landscapes
- 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)
- Separation Using Semi-Permeable Membranes (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Physical Water Treatments (AREA)
Abstract
The invention discloses a kind of processing methods of fluorine-containing recycle-water, the specific steps are as follows: (1) pre-processes；(2) flocculation sedimentation；(3) filtering-reverse osmosis membrane filtration；(4) TOC degradation and ultraviolet sterilization；(5) EDI is handled；(6) TOC degradation and ultraviolet sterilization；(7) secondary filter；It is an advantage of the invention that effluent quality can achieve ultrapure water quality standard, and fluorine removing rate is high, wastewater recycle rate is high, operating cost is low.
Description
Technical field
The invention belongs to field of waste water treatment, more specifically to a kind of processing side of the fluorine-containing recycle-water of electronics industry
Method.
Background technique
With the fast development of electronic product in recent years, the wastewater discharge of electronics industry increasingly increases, additionally due to electric
Sub-industry preparation process is increasingly sophisticated, and the processing difficulty of electronics waste water is also continuously increased.The main source of electronics waste water has at present
Polishing, chemical etching, black/brown oxidation, burr removing, de-smear, plated-through-hole, tin plating, copper facing, stripping tin, anti-welding green paint, develop and at
The processes such as type cleaning, therefore containing there are many substance to be treated for having negative effect to environment in electronics waste water, including
Fluorine ion.By taking the semi-conductor industries units such as photovoltaic cell manufacture, Electronics Factory as an example, wafer etching and quartz will use big when cleaning
Hydrofluoric acid is measured, hydrofluoric acid and ammonium fluoride are wherein contained in etching liquid used in wet etching process, the fluorine ion in cleaning link
It can enter in electronics waste water with pure water, Funing tablet is up to 1000mg/L or more in the acidic fluoride-containing waste water of generation.Fluorine is for people
And the health of animal can all constitute grave danger, will cause the death of people when serious, therefore direct emission these fluoride wastes can
Grave danger can be constituted to environment, in order to avoid the pollution of underground water, soil, surface water, be had to pass through before electronics discharge of wastewater
Fluorine removal processing reaches emission limit, such as " semicon industry pollutant emission standard " (DB31/445- that Shanghai City is existing
2006) regulation fluorine ion emission limit is 20mg/L, existing " water pollutant the comprehensive discharge standard " (DB11/307- in Beijing
2013) it is 10mg/L that regulation, which is discharged into the fluoride limit value of public sewerage treatment system, and the World Health Organization suggests, fluorine in drinking water
The concentration limit of compound is 1.5mg/L.
The processing method of existing fluoride waste mainly has the precipitation method, absorption method, electrochemical process and membrane processing method.Precipitation method master
If adding substance (lime, neutral calcium salt, aluminium salt, molysite for generating precipitating with cohesion ability or with fluoride in waste water
And PAM etc.), form a large amount of colloidal substances or precipitating, fluoride is also agglomerated or is precipitated therewith, then by filtering by fluorine ion from water
The process of middle removing；This method is simple, convenient, at low cost, processing wastewater flow rate is big, water outlet is substantially up to discharge of wastewater mark (10-
20mg/L), but it is not suitable for drinking-water processing, is suitable for industrial application, and reaction speed is slow, reaction process waste residue amount is big, individually locates
Shipwreck is managed out lower than 10mg/L.Absorption method is that specific adsorbent is selected to be added to a kind of means for carrying out fluorine removal in waste water,
Basic process includes following four step: (1) solute molecule is diffused into suction by the boundary layer of adsorbent surface from solution main body
Attached dose of outer surface, referred to as external diffusion；(2) solute molecule through hole is spread, and moves to adsorbent micropore from adsorbent outer surface
Inside, referred to as in diffusion；(3) diffusion into the surface of the fluorine ion along hole surface；(4) fluorine ion is attracted on hole surface.It is typical
The active metal oxide of adsorbent, zeolites and resin；But reactive metal oxides regeneration is complicated, it be in 420-
Calcination is carried out at 1000 DEG C, for zeolite as de-fluoridation adsorbent, adsorption capacity is lower, and dosage is big, and adsorption time is long, so only
Suitable for the processing of rural area fluorinated water, and the use of large-scale processing equipment is not suitable for it；Ion exchange resin is in fluorine removal
In the process, defluorination effect can be influenced by other minerals in waste water, decline effluent characteristics；And resin is easy to be miscellaneous by other
Matter pollution, causes defluorination effect to be deteriorated.Electrodialysis be under DC electric field effect, using the selective penetrated property of amberplex,
Charged ion penetrates amberplex directional migration, separates from aqueous solution and other not charged components, thus realization pair
The purpose of concentration, desalination, purification and the purification of solution.Equipment is simple, operation is easy, stable, can continuous water processed, be easy to reality
The features such as now automatically controlling fluorine removal is completely thorough, and effluent characteristics are fine, can automatic operation, management is easier；Suitable for original
Water salt content in 1-5g/L fluorinated volume in 5mg/L high fluorine bitter below, with being suitable for ground Kucheng's water such as northwest China, Shandong
The concentration removal of fluorine from water engineering in area；But it is stringent to water quality requirement, raw water need to be pre-processed；Processing cost is expensive (about
6 yuan/t water), equipment investment is big；Other Hubeiwans are eliminated, fluorine removing rate is to be improved；There are film polarization to tie for technical aspect
Dirt, the type of film and service life wait to study；Energy consumption is high, and operation is not sufficiently stable and with reasons such as the fast developments of RO, at film
Logos is to be made in the solution of side using film made of organic polymer or inorganic material using the concentration difference of film two sides solution
Solute or solvent penetration to the other side, to achieve the purpose that separate solute with solvent.The advantages of UF membrane is separation effect
Fruit is good.However the disadvantages such as membrane separation technique also has its limitation, need to pre-process to solution, and treating capacity is low.
Based on above-mentioned factor, when facing fluoride waste, start to have occurred combining combination technique, for example disclose (bulletin) number
For CN105036406A, in the Chinese invention patent application file that open (bulletin) day is 2015-11-11, disclose a kind of new
Type FLUORIDE REMOVAL IN WASTEWATER technique is maximally utilising original technique, equipment, and spent acid removes most of heavy metal by vulcanization process
After pollutant, enters gypsum process and carry out preneutralization, gypsum filtrate (liquid can be controlled in 60~100mg/l or less containing F.So
Gypsum filtrate is neutralized using carbide slag afterwards, addition flocculant flocculation, filtering, to remove the heavy metal pollution in waste water
Object can make Funing tablet in flocculation filtrate can be controlled in 20~40mg/L or less.Then be added aluminum sulfate solution Absorptive complex wave fluorine from
F concentration in waste water can be down to 5mg/L hereinafter, other elements are up to standard by son.But above scheme still have reaction speed it is slow,
The problems such as reaction process waste residue amount is big；For another example disclosing (bulletin) number is CN101121554A, and open (bulletin) day is 2008-02-
In 13 Chinese invention patent application file, the defluorination method of a kind of electroosmose process and the integrated application of absorption method is disclosed, it is this
Defluorination method is carried out by following procedure: defluorinating agent of the 1. selected adsorbent capacity greater than 5mg/g simultaneously installs mechanical filter, fluorine removal
Column tank, accurate filter, flowmeter are connected to pipe fitting and shut-off valve with holding vessel, and water fluoride content control is in 0.0- after fluorine removal
1.8mg/L；2. mechanical filter, accurate filter and the flowmeter of electric dialyzator and pre-treatment are installed, with pipe fitting and cut-off
Valve is connected to holding vessel, and water fluoride content control is in 0.0-1.8mg/L after fluorine removal；3. installation holding vessel indicated on tank body scale and
Moisture storage capacity；4. opening the fluorine removal device of absorption method type and electroosmose process type, calculated with a kind of water fluoride content of defluorination method another
A kind of water fluoride content of defluorination method regulates and controls the ratio that the two flows into holding vessel with flowmeter；5. allotment: such as using electric osmose at 1: 1
Fluorine content is 0.2mg/L in analysis method water, is exactly 1.6mg/L with absorption method water fluoride content, and so on.The fluorine removal of above-mentioned integrated-type
Method ratio is significantly improved with single method for removing fluor water utilization rate, but still requires that fluorinated volume is in 0.0- in water before its electrodialysis
1.8mg/L, it is stringent to water quality requirement, raw water need to be pre-processed, improve processing cost, and effluent quality is not able to satisfy
Electronics industry ultrapure water is required with water.
In addition the ultrapure of a large amount of high water quality levels is needed in current photovoltaic industry, integrated circuit industry and semicon industry
Water is used to rinse, such as in the process flow of semiconductor devices preparation, and the link that silicon wafer rinses according to statistics accounts for overall process step
As many as 17%.In electronics industry, common tap water prepares ultrapure water as raw water, and the great demand of ultrapure water makes certainly
Water water rate becomes a part very important in ultrapure water preparation cost.If therefore the waste water of electronics industry is reachable after processing
Cost to ultrapure water production system raw water water water quality requirement, ultrapure water preparation can decline to a great extent, to reduce electronics production
The cost of product production.
Regulation in " electronics and semi-conductor industry ultrapure water water quality requirement ASTM D5127-13 (2018) ", line width is 0.5
The content of fluorine should control within 0.1ug/L in microelectronics production equipment water between~1.0um.This is because in ultrapure water
The presence of fluorine may will affect the quality of production product, and in wafer manufacturing process, fluorine is cause key mat to break down main
Pollutant, fluoride pollution can cause the corrosion and defect of aluminium keypad, to influence the quality of the microchip of manufacture.For another example manufacture is integrated
In the process flow of circuit (IC), ultrapure water be mainly used for removing its surface contaminant (particle) and wet process pickling process it
Post processing circuitry plate, circuit board can pass through the circular treatment of 50 ultrapure waters, therefore water intermediate ion impurity can be to final products
Quality has a negative impact.Silicon plate atom on circuit board surface has a large amount of unsaturated bonds, therefore has very high
Chemical activity and corresponding adsorption property, the inorganic pollution of Adsorption on Surface will increase the defect of sedimentary, and defect can expand
It is scattered in block, so as to cause fault of construction.Ionic soil can caused by closure between conductor, corrode conductor, lead to IP layers
Topological pattern distortion etc..Therefore in the water outlet of reuse electronics waste water treatment process, it should be ensured that ultrapure water production system energy
It is enough to have certain removal effect to the fluorine in recycle-water, so that it is met electronics and semi-conductor industry ultrapure water water quality requirement.And it is current
Fluorinion concentration is often mg/L grades in the water outlets of defluorinating process such as the common precipitation method, absorption method, electrochemical process and membrane processing method
Not, it is not able to satisfy electronics industry ultrapure water water requirement.
Therefore, it is imperative to develop a kind of practicable defluorination method.
Summary of the invention
1. to solve the problems, such as
In view of the above-mentioned problems, the present invention provides a kind of processing method of fluorine-containing recycle-water, by chemical precipitation, flocculation sedimentation with
EDI water treatment technology combines, and water outlet fluorinated volume is extremely low, can achieve ultrapure water quality standard, and fluorine removing rate is high, wastewater recycle rate
Height, operating cost are low.
2. technical solution
To solve the above-mentioned problems, the technical solution adopted in the present invention is as follows:
A kind of processing method of fluorine-containing recycle-water, comprises the following steps:
(1) it pre-processes: introducing excess calcium hydroxide and calcium chloride solution in the fluoride waste for being 8~9 to pH value, generate fluorine
Change calcium, adjusts water inlet pH value；
Herein it should be noted that needing in advance to detect the water quality of waste water (mainly pH and fluorine content), about " pH
The fluoride waste that value is 8~9 " can be the original waste water without acid-base accommodation, be also possible on demand by acid-base accommodation
Waste water；According further to the fluorine content detected, excessive calcium ion is introduced into water body, " excess " described herein refers to useless
The fluorine contained in water is benchmark, and the amount of additional calcium ion is more than the theory demands amount for precipitating fluorine ion completely.
(2) coagulant is added into pretreated waste water, then, the pH value for adjusting waste water is 6-7, is re-introduced into flocculation
Agent；
(3) it filters, the waste water after flocculation sedimentation takes supernatant, and filtering is (miscellaneous using solid in cartridge filter removal waste water
Matter), then, reverse osmosis treatment is carried out using reverse osmosis membrane filtration；
(4) TOC degradation and ultraviolet sterilization, (utilizing TOC Degradator) are discharged reverse osmosis membrane and carry out TOC degradation treatment,
Again through ultraviolet treatment with irradiation；
(5) EDI is handled, and is handled by electrodeionization system waste water, the tree filled in the electrodeionization system
Rouge, which is negative, is loaded with the expanded polystyrene resin (HZO-201) of nano hydrated zirconium oxide；
(6) TOC degradation and ultraviolet sterilization, (utilize TOC Degradator, Degradator using 185nm ultraviolet light) it is right
EDI water outlet carries out TOC degradation treatment, then handles through ultraviolet light irradiation-sterilize；
(7) accurate filter: water after ultraviolet treatment with irradiation with accurate filter (using PP matter spray fusing formula filter core,
Filter core precision 5um) it is filtered.
Preferably, in step (1), on the basis of the fluorinated volume in waste water, the mass concentration that adds of calcium hydroxide is The mass concentration that adds of calcium chloride isThe unit of the mass concentration is mg/L, introducing
Calcium hydroxide and calcium chloride can occur chemical precipitation with fluorine ion and react, generate calcirm-fluoride.
Preferably, in step (2), the coagulant is PAC, on the basis of the mass concentration of fluorine in water body, dosage
For CPAC=4CF -；The flocculant is PAM, on the basis of the mass concentration of fluorine in water body, dosage CPAM=4CF -.Step
In rapid, first plus flocculant, then pH reconciled, the CaF generated in step (1) can be made2Precipitating is converted to larger particles, then draws again
Enter flocculant, sedimentation effect can be enhanced.
Preferably, in step (4), the ultraviolet light irradiation is specially to be dropped using UV-254nm ultraviolet sterilizer to TOC
Water outlet after solution is handled.
Primary filtration first is carried out to the supernatant of flocculation sedimentation in step (3), it is therefore an objective to remove solid impurity in waste water；It connects
Waste water is handled using reverse osmosis membrane, it is therefore an objective to remove the dissolubilities such as sodium, calcium, magnesium, chloride, nitrate, carbonate
Substance；Reverse osmosis membrane water outlet is handled with TOC Degradator in step (4), is urged by the UV-185nm ultraviolet light of high dose
Change, hydroxyl radical free radical is generated in water, to organic matter, ozone, chlorine and the chloramines oxidative degradation in water, to reduce in water
TOC content；Using UV-254nm ultraviolet sterilizer, can degrade to TOC water outlet further disinfection.
Preferably, in step (5), the EDI processing carries out level-one EDI processing (its specifically, being first discharged to step (4)
The resin in electrodeionization system utilized is gel-type epistasis resin), it is therefore an objective to the gas and boron that are dissolved in water body and
Silica is removed；Then second level EDI processing is carried out again, is filled in the electrodeionization system of the second level EDI processing
Resin, which is negative, is loaded with the expanded polystyrene resin of nano hydrated zirconium oxide, it is therefore an objective to the further removal rate for improving fluorine.This
Locating the load has the expanded polystyrene resin of nano hydrated zirconium oxide (described is loaded with the porous of nano hydrated zirconium oxide
Polystyrene resin is bibliography, Xu Jingsheng, the preparation of the resin-carried nano hydrated zirconium oxide of expanded polystyrene and its is removed
Fluorine performance study, the HZO-201 in 2014-05-28).
Preferably, in step (5), when the second level EDI is handled, fluorinion concentration is 0-5mg/L in water inlet.In addition, its
His specific processing parameter is as follows: water inlet pH value is 5.8-8.0；Temperature is 5-35 DEG C；Intake pressure is 1.5-4kg/cm2。
Preferably, in step (6), the TOC degradation and the same step of ultraviolet sterilization process (4).
Preferably, in step (7), the filtering accuracy of accurate filter is 5um.
A kind of ultrapure water is prepared using the processing method of above-mentioned fluorine-containing recycle-water.
The application of above-mentioned ultrapure water is applied in the technique of manufacture integrated circuit, the cleaning to circuit board.
3. beneficial effect
Compared with the prior art, the invention has the benefit that
(1) the present invention provides a kind of processing methods of fluorine-containing recycle-water, handle fluoride waste (especially using this technology
Fluoride waste in electronics industry), there is following advantage: first, the removal rate of fluorinion in waste water is high, the water of ultrapure water can be reached
It is flat；Second, fluoride ion removing is high-efficient；Third, the recovery utilization rate of waste water can be greatly improved, ultrapure water preparation is significantly reduced
System operation cost；
(2) the present invention provides a kind of processing methods of fluorine-containing recycle-water, firstly, carrying out flocculation sedimentation, filtering to waste water
Processing, can remove CaF2Solid impurity in particle and other waste water is precipitated, the blocking of permeable membrane in next step is prevented；Then,
Waste water is handled using reverse osmosis membrane, the dissolved matters such as removal sodium, calcium, magnesium, chloride, nitrate, carbonate reduce
Water body hardness prevents calcium and magnesium dirt from influencing subsequent processing steps；Then, then water outlet is handled using level-one EDI technology, it is right
The gas and boron and silica of dissolution are removed；Followed by the porous polyphenyl for having nano hydrated zirconium oxide filled with load
The second level EDI system of vinyl handles waste water, further reduced Fluoride Concentration In Waters；Finally, being carried out to water body
TOC bis- times degradations, ultraviolet sterilizations, that is, secondary filter, make effluent quality reach the level of ultrapure water；
(3) in existing ultrapure water production system, foreign ion in raw water is removed usually using RO/EDI integrated technology,
But above-mentioned technical treatment object is mostly tap water.And in patent application document it is the electronics waste water containing fluorine ion, wherein containing
For some fluorine ions since radius is smaller, the usual content of fluorine ion in reverse osmosis membrane water outlet is still higher, and for conventional EDI
Technology, when ion exchange resin is using foreign ion in ion exchange principle removal waste water, since fluorine ion sequence is more leaned on
Afterwards, thus the removal effect of fluorine ion will receive sulfate radical, nitrate anion, chromate, bromide ion, cryanide ion, chloride ion etc. yin from
The influence of son, and a large amount of anion are usually contained in electronics waste water, therefore in reuse electronics waste water as ultrapure water production system original
When water, EDI technology defluorination effect is unsatisfactory；
Based on this, the present invention provides a kind of processing methods of fluorine-containing recycle-water, carry out level-one EDI processing and two to water body
Method associated with grade EDI processing, handles fluoride waste；In the second level EDI system of processing, used resin is load
There is the expanded polystyrene resin of nano hydrated zirconium oxide, has the advantage that first, in ion exchange resin, ion exchange
The polarization in interface diffusion layer that film is contacted with water phase makes water decomposition at hydrogen ion and hydroxide ion, they are in addition to load current
Outside, it is also used to the regeneration of resin, the nano hydrated zirconium oxide loaded on resin enhances the electric conductivity of resin, so that more
Hydrogen ion and hydroxide ion can be used for regenerating resin, ensure that the regeneration rate of resin；Second, in conventional EDI technology,
Water dissociates under electric field action generates hydrogen ion and hydroxide ion, and the dissociation of these ion a part is used for resin regeneration, another
Part is for undertaking electric current.The load used in this technology has the expanded polystyrene resin of nano hydrated zirconium oxide, in resin
On loaded nano hydrated zirconium oxide reinforced resin electric conductivity so that hydrogen ion and hydroxide ion that more water electrolysis generates are used
In resin regeneration, to just improve ion exchange resin for the removal effect of foreign ion, the fluorine removal except fluororesin is enhanced
Effect；
(4) there is the expanded polystyrene resin technology of Fluoride Removal of nano hydrated zirconium oxide for having load, in use process
Fluorine removal for a period of time after, need using desorbing agent to being desorbed except fluororesin, the desorption and regeneration of resin can greatly increase tree
Operating cost when rouge fluorine removal.In order to improve the feasibility that this obligate fluorine removal Resin Industryization is promoted, this technology by electrodialysis with
Ion exchange resin, which combines, can be achieved to save desorption and regeneration institute in resin use process to the novel cyclic regeneration except fluororesin
The expense needed, greatly reduce it is obligate except fluororesin fluorine removal when operating cost.
Specific embodiment
The present invention is further described below combined with specific embodiments below.
Embodiment 1
The present embodiment takes certain micro-electronic manufacturing factory fluoride waste 2L with electronics industry fluoride waste, and raw water pH value is 2.84,
COD concentration is 86mg/L, and fluorinion concentration is that 364mg/L is that (present invention is measured object using direct ion electrodes selective method
Fluorinion concentration in water outlet, Monitoring lower-cut are 15.1 μ g/L), waste water is handled using processing method of the invention, is had
Steps are as follows for body:
(1) waste water pH value is adjusted to 8~9, is introduced excess calcium hydroxide and calcium chloride solution thereto, is brought it about chemistry
Precipitation reaction generates calcirm-fluoride.
(2) flocculation sedimentation, step (1) Xiang Fasheng chemical precipitation reaction after waste water in introduce coagulant PAC so that carefully
Small precipitating generates larger particles, and waste water PH is adjusted to 6~7 later, is re-introduced into flocculant PAM enhancing sedimentation effect.
(3) supernatant in step (2) is taken, after solid impurity in cartridge filter removal waste water, waste water is passed through anti-
Permeable membrane removes the dissolved matters such as sodium, calcium, magnesium, chloride, nitrate, carbonate.
(4) TOC degradation and ultraviolet sterilization, (utilizing TOC Degradator) are discharged reverse osmosis membrane and carry out TOC degradation treatment,
Again through ultraviolet treatment with irradiation, hydroxyl radical free radical can be generated in water by the UV-185nm ultraviolet catalytic of high dose, it is right
Organic matter in water carries out oxidative degradation, to reduce the TOC content in water；
The water outlet after TOC degradation is handled using UV-254nm ultraviolet sterilizer.
(5) EDI is handled, and to water outlet in step (4), is handled by electrodeionization system waste water, the electricity go from
The resin filled in subsystem, which is negative, is loaded with the expanded polystyrene resin of nano hydrated zirconium oxide；Its specific processing parameter is such as
Under: water inlet pH value is 5.8-8.0；Temperature is 5-35 DEG C；Intake pressure is 1.5-4kg/cm2。
It is as shown in table 1 by EDI processed waste water water quality:
1 EDI processed waste water water quality of table
(6) TOC degradation and ultraviolet sterilization, (utilizing TOC Degradator) is discharged EDI and carries out TOC degradation treatment, then passes through
UV-254nm ultraviolet sterilizer carries out disinfection.
(7) accurate filter: water after ultraviolet treatment with irradiation with accurate filter (using PP matter spray fusing formula filter core,
Filter core precision 5um) it is filtered.
Total effluent quality is as shown in table 2:
The total effluent quality of table 2
"-" indicates that fluorine ions in water body concentration is lower than 15.1 μ g/L of Monitoring lower-cut in table.
It can be seen from the data of table 1 and table 2 through the invention after the processing of newly developed technology of Fluoride Removal, fluorine in wastewater from
For sub- removal rate up to 95%, waste water further passes through TOC Degradator, polishing mixed bed, ultraviolet ray disinfector, accurate filter depth
After processing, the presence of fluorine ion, removal rate of the entire technique to fluorine ion are not detected using direct ion electrodes selective method
Reach 99% or more, effluent quality meets electronics industry ultrapure water water requirement.
Embodiment 2
The present embodiment takes certain micro-electronic manufacturing factory fluoride waste 2L with electronics industry fluoride waste, and raw water pH value is 2.84,
COD concentration is 86mg/L, and fluorinion concentration is that 364mg/L is that (present invention is measured object using direct ion electrodes selective method
Fluorinion concentration in water outlet, Monitoring lower-cut are 15.1 μ g/L), waste water is handled using processing method of the invention, is had
Steps are as follows for body:
(1) waste water pH value is adjusted to 8~9, introduces excess calcium hydroxide and calcium chloride solution thereto, it is heavy to bring it about chemistry
Reaction of forming sediment generates calcirm-fluoride；On the basis of the mass concentration of fluorine in water body, the dosage of the calcium hydroxide is
The dosage of calcium chloride is
(2) flocculation sedimentation, step (1) Xiang Fasheng chemical precipitation reaction after waste water in introduce coagulant PAC so that carefully
Small precipitating generates larger particles, and waste water PH is adjusted to 6~7 later, is re-introduced into flocculant PAM enhancing sedimentation effect；The coagulation
Agent is PAC, on the basis of the mass concentration of fluorine in water body, dosage CPAC=4CF -；The flocculant is PAM, with water body
On the basis of the mass concentration of middle fluorine, dosage CPAM=4CF -.After the processing of this step, the pH of water outlet is that 7.96, COD is
41mg/L, fluorinion concentration 3.2mg/L.
(3) supernatant in step (2) is taken, after solid impurity in cartridge filter removal waste water, waste water is passed through anti-
Permeable membrane removes the dissolved matters such as sodium, calcium, magnesium, chloride, nitrate, carbonate.
(4) reverse osmosis membrane water outlet is handled using TOC Degradator (UV-185nm low-pressure high-energy ultraviolet technology), then
In conjunction with UV-254nm ultraviolet sterilizer, hydroxyl can be generated in water certainly by the UV-185nm ultraviolet catalytic of high dose
By base, oxidative degradation is carried out to the organic matter in water, to reduce the TOC content in water；
It carries out disinfection again through UV-254nm ultraviolet sterilizer.
(5) EDI is handled, to water outlet in step (4), first with the electrodeionization system pair for being filled with gel-type epistasis resin
Waste water carries out level-one EDI processing；Its specific processing parameter is as follows: water inlet pH value is 5.8-8.0；Temperature is 5-35 DEG C；Influent pressure
Power is 1.5-4kg/cm2；
Then the electrodeionization system pair for the expanded polystyrene resin for having nano hydrated zirconium oxide filled with load is utilized
Waste water carries out second level EDI processing, and specific processing parameter is as follows: water inlet pH value is 5.8-8.0；Temperature is 5-35 DEG C；Influent pressure
Power is 1.5-4kg/cm2.It is as shown in table 3 by EDI processed waste water water quality:
3 EDI processed waste water water quality of table
(6) by EDI treated waste water by second level TOC Degradator, polishing mixed bed, UV-254nm ultraviolet sterilizer into
Row disinfection.
(7) accurate filter: water after ultraviolet treatment with irradiation with accurate filter (using PP matter spray fusing formula filter core,
Filter core precision 5um) it is filtered, the electronic grade ultrapure water of high resistivity is prepared, effluent quality is as shown in table 4:
The total effluent quality of table 4
"-" indicates that fluorine ions in water body concentration is lower than 15.1 μ g/L of Monitoring lower-cut in table.
It can be seen from the data of table 3 and table 4 through the invention after the processing of newly developed technology of Fluoride Removal, fluorine in wastewater from
For sub- removal rate up to 95%, waste water further passes through TOC Degradator, polishing mixed bed, ultraviolet ray disinfector, 0.1um barrel type filtering
After the advanced treating of device and ultrafiltration module, the presence of fluorine ion, entire work are not detected using direct ion electrodes selective method
Skill reaches 99% or more to the removal rate of fluorine ion, and effluent quality meets electronics industry ultrapure water water requirement.
Embodiment 3
The present embodiment takes certain micro-electronic manufacturing factory fluoride waste 2L with electronics industry fluoride waste, and raw water pH value is 2.84,
COD concentration is 86mg/L, and fluorinion concentration is that 364mg/L is that (present invention is measured object using direct ion electrodes selective method
Fluorinion concentration in water outlet, Monitoring lower-cut are 15.1 μ g/L), waste water is handled using processing method of the invention, is had
Steps are as follows for body:
(1) waste water pH value is adjusted to 8~9, introduces excess calcium hydroxide and calcium chloride solution thereto, it is heavy to bring it about chemistry
Reaction of forming sediment generates calcirm-fluoride；On the basis of the mass concentration of fluorine in water body, the dosage of the calcium hydroxide is
The dosage of calcium chloride is
(2) flocculation sedimentation, step (1) Xiang Fasheng chemical precipitation reaction after waste water in introduce coagulant PAC so that carefully
Small precipitating generates larger particles, and waste water PH is adjusted to 6~7 later, is re-introduced into flocculant PAM enhancing sedimentation effect.
(3) supernatant in step (2) is taken, after solid impurity in cartridge filter removal waste water, waste water is passed through anti-
Permeable membrane removes the dissolved matters such as sodium, calcium, magnesium, chloride, nitrate, carbonate.
(4) TOC degradation and ultraviolet sterilization, (utilizing TOC Degradator) are discharged reverse osmosis membrane and carry out TOC degradation treatment,
Again through ultraviolet treatment with irradiation, hydroxyl radical free radical can be generated in water by the UV-185nm ultraviolet catalytic of high dose, it is right
Organic matter in water carries out oxidative degradation, to reduce the TOC content in water；
The water outlet after TOC degradation is handled using UV-254nm ultraviolet sterilizer.
(5) EDI is handled, and to water outlet in step (4), is handled by electrodeionization system waste water, the electricity go from
The resin filled in subsystem, which is negative, is loaded with the expanded polystyrene resin of nano hydrated zirconium oxide；Its specific processing parameter is such as
Under: water inlet pH value is 5.8-8.0；Temperature is 5-35 DEG C；Intake pressure is 1.5-4kg/cm2。
(6) TOC degradation and ultraviolet sterilization, (utilizing TOC Degradator) is discharged EDI and carries out TOC degradation treatment, then passes through
UV-254nm ultraviolet sterilizer carries out disinfection.
(7) accurate filter: water after ultraviolet treatment with irradiation with accurate filter (using PP matter spray fusing formula filter core,
Filter core precision 5um) it is filtered.
After processing, the presence of fluorine ion is not detected using direct ion electrodes selective method, entire technique is to fluorine ion
Removal rate reach 95% or more, effluent quality meets electronics industry ultrapure water water requirement.
Embodiment 4
The present embodiment takes certain micro-electronic manufacturing factory fluoride waste 2L with electronics industry fluoride waste, and raw water pH value is 2.84,
COD concentration is 86mg/L, and fluorinion concentration is that 364mg/L is that (present invention is measured object using direct ion electrodes selective method
Fluorinion concentration in water outlet, Monitoring lower-cut are 15.1 μ g/L), waste water is handled using processing method of the invention, is had
Steps are as follows for body:
(1) waste water pH value is adjusted to 8~9, is introduced excess calcium hydroxide and calcium chloride solution thereto, is brought it about chemistry
Precipitation reaction generates calcirm-fluoride.
(2) flocculation sedimentation, step (1) Xiang Fasheng chemical precipitation reaction after waste water in introduce coagulant PAC so that carefully
Small precipitating generates larger particles, and waste water PH is adjusted to 6~7 later, is re-introduced into flocculant PAM enhancing sedimentation effect；The coagulation
Agent is PAC, on the basis of the mass concentration of fluorine in water body, dosage CPAC=4CF -；The flocculant is PAM, with water body
On the basis of the mass concentration of middle fluorine, dosage CPAM=4CF -。
(3) supernatant in step (2) is taken, after solid impurity in cartridge filter removal waste water, waste water is passed through anti-
Permeable membrane removes the dissolved matters such as sodium, calcium, magnesium, chloride, nitrate, carbonate.
(4) TOC degradation and ultraviolet sterilization, (utilizing TOC Degradator) are discharged reverse osmosis membrane and carry out TOC degradation treatment,
Again through ultraviolet treatment with irradiation, hydroxyl radical free radical can be generated in water by the UV-185nm ultraviolet catalytic of high dose, it is right
Organic matter in water carries out oxidative degradation, to reduce the TOC content in water；
The water outlet after TOC degradation is handled using UV-254nm ultraviolet sterilizer.
(5) EDI is handled, and to water outlet in step (4), is handled by electrodeionization system waste water, the electricity go from
The resin filled in subsystem, which is negative, is loaded with the expanded polystyrene resin of nano hydrated zirconium oxide；Its specific processing parameter is such as
Under: water inlet pH value is 5.8-8.0；Temperature is 5-35 DEG C；Intake pressure is 1.5-4kg/cm2。
(6) TOC degradation and ultraviolet sterilization, (utilizing TOC Degradator) is discharged EDI and carries out TOC degradation treatment, then passes through
UV-254nm ultraviolet sterilizer carries out disinfection.
(7) accurate filter: water after ultraviolet treatment with irradiation with accurate filter (using PP matter spray fusing formula filter core,
Filter core precision 5um) it is filtered.
After processing, the presence of fluorine ion is not detected using direct ion electrodes selective method, entire technique is to fluorine ion
Removal rate reach 95% or more, effluent quality meets electronics industry ultrapure water water requirement.
Comparative example 1
Substantially with embodiment 2, its difference place is only that this comparative example:
Level-one EDI in step (5) handles (resin filled identical as the electrodeionization system that second level EDI is handled
It is gel-type epistasis resin)
It is as shown in table 5 by EDI processed waste water water quality:
5 EDI processed waste water water quality of table
The total effluent quality of table 6
It can be seen from the data of table 5 and table 6 by conventional EDI technology to reuse fluoride wastewater treatment after, fluorine in wastewater
Ion remaval rate is 23%, and waste water further passes through TOC Degradator, polishing mixed bed, ultraviolet ray disinfector, 0.1um cartridge type mistake
After the advanced treating of filter and ultrafiltration module, effluent quality is unsatisfactory for electronics industry ultrapure water water requirement.Therefore, if will pass through
Preliminary fluorine removal treated fluoride waste carries out reuse as ultrapure water system raw water, is surpassed using what is be made of conventional EDI device
The ultrapure water for meeting industry production needs can not be prepared in pure water making system, therefore recycles needs pair when fluoride waste
Ultrapure water production system is further improved.
Comparative example 2
Substantially with embodiment 2, its difference place is only that this comparative example:
EDI processing technique is substituted for electrodialysis process method in the step (5).
Primary condition are as follows: use punch die formula partition electric dialyzator 400*800mm, 150 pairs of films, three sections of three-level assemblings；
Select polyethylene heterogeneous membrane.
Water quality before and after 7 electrodialysis process of table
The total effluent quality of table 8
It can be seen from the data of table 7 and table 8 by conventional electrodialytic technique to reuse fluoride wastewater treatment after, waste water
Middle fluoride ion removing rate is only 14%, even if waste water further passes through TOC Degradator, polishing mixed bed, and ultraviolet ray disinfector,
After the advanced treating of 0.1um cartridge filter and ultrafiltration module, content of fluoride ion is still more, and effluent quality is unsatisfactory for electronics industry
Ultrapure water is required with water.It therefore, if will treated that fluoride waste is returned as ultrapure water system raw water by preliminary fluorine removal
With can not be prepared using the ultrapure water production system being made of conventional electrodialysis plant and meet the super of industry production needs
Pure water.
Claims (9)
1. a kind of processing method of fluorine-containing recycle-water, which is characterized in that comprise the following steps:
(1) it pre-processes, excess calcium hydroxide and calcium chloride is introduced in the fluoride waste for being 8~9 to pH value；
(2) coagulant is added into pretreated water body for flocculation sedimentation, and then, the pH value for adjusting waste water is 6-7, is re-introduced into
Flocculant；
(3) it filters, the waste water after flocculation sedimentation takes supernatant, filters, and then, carries out reverse osmosis treatment using reverse osmosis membrane；
(4) TOC degradation and ultraviolet sterilization are discharged reverse osmosis membrane and carry out TOC degradation and the processing of ultraviolet light irradiation-sterilize；
(5) EDI is handled, and by electrodeionization system, to ultraviolet light irradiation-sterilize, treated that water body is handled, and the electricity is gone
The resin filled in ion system, which is negative, is loaded with the expanded polystyrene resin of nano hydrated zirconium oxide；
(6) TOC degradation and ultraviolet sterilization, are discharged EDI and carry out TOC degradation treatment, then handle through ultraviolet light irradiation-sterilize；
(7) secondary filter, water body is filtered using accurate filter after ultraviolet treatment with irradiation.
2. the processing method of fluorine-containing recycle-water according to claim 1, which is characterized in that in step (1), with fluorine in water body
On the basis of mass concentration, the dosage of the calcium hydroxide isThe dosage of calcium chloride is
3. the processing method of fluorine-containing recycle-water according to claim 1, which is characterized in that in step (2), the coagulant
For PAC, on the basis of the mass concentration of fluorine in water body, dosage CPAC=4CF -；The flocculant is PAM, in water body
On the basis of the mass concentration of fluorine, dosage CPAM=4CF -。
4. the processing method of fluorine-containing recycle-water according to claim 1, which is characterized in that in step (4), the ultraviolet light
Irradiation is specifically, handle the water outlet after TOC degradation using UV-254nm ultraviolet sterilizer.
5. the processing method of fluorine-containing recycle-water according to claim 1, which is characterized in that in step (5), at the EDI
Reason carries out level-one EDI processing specifically, being first discharged to step (4), then carries out second level EDI processing, the second level EDI processing again
Electrodeionization system in the resin filled be negative and be loaded with the expanded polystyrene resin of nano hydrated zirconium oxide.
6. the processing method of fluorine-containing recycle-water according to claim 5, which is characterized in that in step (5), the second level
The fluorinion concentration upper limit is 5mg/L in the water inlet of EDI processing.
7. the processing method of fluorine-containing recycle-water according to claim 1, which is characterized in that in step (7), accurate filter
Filtering accuracy be 5um.
8. a kind of ultrapure water, which is characterized in that prepared using the processing method of the fluorine-containing recycle-water as claimed in claim 1 to 7
It obtains.
9. the application of ultrapure water as claimed in claim 8, which is characterized in that be applied to the technique of manufacture integrated circuit
In, the cleaning to circuit board.
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