CN110451704B - Method for treating fluorine-containing reuse water - Google Patents
Method for treating fluorine-containing reuse water Download PDFInfo
- Publication number
- CN110451704B CN110451704B CN201910815633.0A CN201910815633A CN110451704B CN 110451704 B CN110451704 B CN 110451704B CN 201910815633 A CN201910815633 A CN 201910815633A CN 110451704 B CN110451704 B CN 110451704B
- Authority
- CN
- China
- Prior art keywords
- water
- fluorine
- treatment
- wastewater
- treating
- 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.)
- Active
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 137
- 239000011737 fluorine Substances 0.000 title claims abstract description 111
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 111
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 238000000034 method Methods 0.000 title claims abstract description 85
- 239000002351 wastewater Substances 0.000 claims abstract description 107
- 230000015556 catabolic process Effects 0.000 claims abstract description 44
- 238000006731 degradation reaction Methods 0.000 claims abstract description 44
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 39
- 239000012498 ultrapure water Substances 0.000 claims abstract description 39
- 239000012528 membrane Substances 0.000 claims abstract description 28
- 230000001954 sterilising effect Effects 0.000 claims abstract description 22
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 19
- 238000004659 sterilization and disinfection Methods 0.000 claims abstract description 18
- 238000001914 filtration Methods 0.000 claims abstract description 15
- 230000001376 precipitating effect Effects 0.000 claims abstract description 8
- 230000003311 flocculating effect Effects 0.000 claims abstract description 6
- -1 fluorine ions Chemical class 0.000 claims description 42
- 229920005989 resin Polymers 0.000 claims description 31
- 239000011347 resin Substances 0.000 claims description 31
- 230000008569 process Effects 0.000 claims description 23
- 238000009296 electrodeionization Methods 0.000 claims description 16
- 238000001556 precipitation Methods 0.000 claims description 16
- 229920005990 polystyrene resin Polymers 0.000 claims description 15
- 229910021512 zirconium (IV) hydroxide Inorganic materials 0.000 claims description 15
- 238000004519 manufacturing process 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
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 10
- 239000000701 coagulant Substances 0.000 claims description 10
- 239000000920 calcium hydroxide Substances 0.000 claims description 7
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 7
- 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
- 238000005189 flocculation Methods 0.000 claims description 6
- 230000016615 flocculation Effects 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 239000008394 flocculating agent Substances 0.000 claims description 4
- 238000006115 defluorination reaction Methods 0.000 abstract description 17
- 230000008901 benefit Effects 0.000 abstract description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 17
- 230000000694 effects Effects 0.000 description 16
- 150000002500 ions Chemical class 0.000 description 15
- 238000005516 engineering process Methods 0.000 description 14
- 239000000126 substance Substances 0.000 description 13
- 239000012535 impurity Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 11
- 238000009388 chemical precipitation Methods 0.000 description 10
- 238000000909 electrodialysis Methods 0.000 description 10
- 238000001179 sorption measurement Methods 0.000 description 9
- 239000003463 adsorbent Substances 0.000 description 8
- 230000008929 regeneration Effects 0.000 description 8
- 238000011069 regeneration method Methods 0.000 description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 7
- 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
- 229910002651 NO3 Inorganic materials 0.000 description 7
- 239000011575 calcium Substances 0.000 description 7
- 229910052791 calcium Inorganic materials 0.000 description 7
- 229910001634 calcium fluoride Inorganic materials 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
- 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
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 6
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 238000005498 polishing Methods 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000000243 solution Substances 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
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 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
- 239000002244 precipitate Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000001064 degrader Substances 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 235000020188 drinking water Nutrition 0.000 description 3
- 239000003651 drinking water Substances 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
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000003014 ion exchange membrane Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 238000010525 oxidative degradation reaction Methods 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000008399 tap water Substances 0.000 description 3
- 235000020679 tap water Nutrition 0.000 description 3
- 238000000108 ultra-filtration Methods 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- 239000010457 zeolite Substances 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
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052810 boron oxide Inorganic materials 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 239000011532 electronic conductor Substances 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
- 238000009776 industrial production Methods 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 239000010865 sewage Substances 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
- 239000002904 solvent Substances 0.000 description 2
- 238000005406 washing Methods 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 compound 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
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 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
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 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
- 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
- 239000007864 aqueous solution Substances 0.000 description 1
- KIZFHUJKFSNWKO-UHFFFAOYSA-M calcium monohydroxide Chemical compound [Ca]O KIZFHUJKFSNWKO-UHFFFAOYSA-M 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
- 230000001112 coagulating effect Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 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
- 230000000593 degrading effect Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 230000000249 desinfective effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000007646 directional migration Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000010793 electronic waste Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000006703 hydration reaction Methods 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
- 230000010354 integration Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 230000010291 membrane polarization Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000003403 water pollutant Substances 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 method for treating fluorine-containing reuse water, which comprises the following specific steps: (1) pre-treating; (2) flocculating and precipitating; (3) filtering, namely filtering by a reverse osmosis membrane; (4) TOC degradation and ultraviolet sterilization; (5) EDI processing; (6) TOC degradation and ultraviolet sterilization; (7) performing precision filtration; the invention has the advantages that the effluent quality can reach the ultrapure water standard, and the invention has high defluorination efficiency, high wastewater reuse rate and low operation cost.
Description
Technical Field
The invention belongs to the field of wastewater treatment, and particularly relates to a method for treating fluorine-containing reuse water in the electronic industry.
Background
Along with the rapid development of electronic products in recent years, the discharge amount of waste water in the electronic industry is increasing day by day, and in addition, as the preparation process in the electronic industry is becoming more and more complex, the treatment difficulty of the electronic waste water is increasing. At present, the main sources of electronic wastewater comprise procedures of polishing, chemical etching, black/brown oxidation, deburring, glue residue removal, through hole plating, tin plating, copper plating, tin stripping, solder mask, development, molding cleaning and the like, so that the electronic wastewater contains various substances which need to be treated and have negative effects on the environment, wherein the substances comprise fluorine ions. Taking semiconductor industry units such as photovoltaic cell manufacturing, electronic factories and the like as examples, a large amount of hydrofluoric acid is used for wafer etching and quartz cleaning, wherein etching liquid used in a wet etching process contains hydrofluoric acid and ammonium fluoride, fluorine ions enter electronic wastewater along with pure water in a cleaning link, and the concentration of fluorine in generated fluorine-containing acidic wastewater can reach more than 1000 mg/L. Fluorine poses a great threat to the health of people and animals and causes death of people in severe cases, so that the direct discharge of the fluorine-containing wastewater can pose a great threat to the environment, in order to avoid pollution of underground water, soil and surface water, the electronic wastewater needs to be subjected to defluorination treatment before reaching the discharge limit, such as the limit of fluoride discharge in the public sewage treatment system specified by the current semiconductor industry pollutant discharge standard (DB 31/445) 2006 in Shanghai, the limit of fluoride discharge in the public sewage treatment system specified by the current comprehensive water pollutant discharge standard (DB11/307 2013) in Beijing is 10mg/L, and the concentration limit of fluoride in drinking water is 1.5mg/L according to the recommendation of the world health organization.
The existing treatment methods of fluorine-containing wastewater mainly comprise a precipitation method, an adsorption method, an electrochemical method and a membrane treatment method. The precipitation method is mainly a process of adding substances (lime, neutral calcium salt, aluminum salt, iron salt, PAM and the like) which have the coagulation ability or generate precipitation with fluoride into the wastewater to form a large amount of colloid substances or precipitation, coagulating or precipitating the fluoride along with the colloid substances or precipitation, and then filtering to remove fluorine ions from the water; the method has the advantages of simple and convenient operation, low cost, large wastewater treatment amount, effluent basically reaching the wastewater discharge standard (10-20mg/L), suitability for drinking water treatment, suitability for industrial application, low reaction speed, large amount of waste residues in the reaction process, and difficulty in treating the effluent alone lower than 10 mg/L. The adsorption method is a means for removing fluorine by adding a specific adsorbent into wastewater, and the basic process comprises the following four steps: (1) solute molecules diffuse from the bulk of the solution through the boundary layer on the surface of the adsorbent to the outer surface of the adsorbent, referred to as out-diffusion; (2) solute molecules diffuse through pores and migrate from the outer surface of the adsorbent to the interior of the adsorbent pores, referred to as internal diffusion; (3) fluorine ions diffuse along the surface of the pore surface; (4) the fluorine ions are adsorbed on the pore surfaces. Typical adsorbents are active metal oxides, zeolites and resins; however, the regeneration of the active metal oxide is complex, the active metal oxide needs to be burned at the temperature of 420-1000 ℃, and the zeolite is used as a defluorination adsorbent, which has lower adsorption capacity, large dosage and long adsorption time, so the zeolite is only suitable for the treatment of fluorine-containing water in rural areas and is not suitable for the use of large-scale treatment equipment; in the process of removing fluorine by the ion exchange resin, the fluorine removal effect is influenced by other mineral substances in the wastewater, so that the quality of effluent is reduced; and the resin is easily contaminated by other impurities, resulting in deterioration of the defluorination effect. The electrodialysis is to realize the purposes of concentration, desalination, refining and purification of the solution by utilizing the selective permeability of the ion exchange membrane and the directional migration of charged ions through the ion exchange membrane to separate the charged ions from the aqueous solution and other uncharged components under the action of a direct current electric field. The device is simple, the operation is easy, the operation is stable, the water can be continuously produced, the automatic control is easy to realize, and the like, the fluorine removal is clean and thorough, the water outlet quality is good, the automatic operation can be realized, and the management is easy; the method is suitable for high-fluorine brackish water with the salt content of 1-5g/L and the fluorine content of less than 5mg/L of raw water, and is suitable for concentrated drinking water defluorination engineering in northwest and Shandong regions of China; however, the requirement on water quality is strict, and raw water needs to be pretreated; the treatment cost is high (about 6 yuan/ton water), and the equipment investment is large; other beneficial components are removed, and the fluorine removal efficiency needs to be improved; the technical aspects of the method include membrane polarization scaling, and the type and the service life of the membrane are yet to be researched; the membrane treatment method is to use a membrane made of organic polymer or inorganic material to permeate solute or solvent in solution on one side to the other side by using the concentration difference of the solution on the two sides of the membrane so as to achieve the purpose of separating the solute from the solvent. The membrane separation has the advantage of good separation effect. However, the membrane separation technology has the defects of limitation, pretreatment of the solution, low treatment capacity and the like.
Based on the factors, when the fluorine-containing wastewater is treated, a combined process begins to appear, for example, in the Chinese invention patent application document with the publication (announcement) number of CN105036406A and the publication (announcement) date of 2015-11-11, a novel wastewater fluorine removal process is disclosed, the original process and equipment are utilized to the maximum extent, waste acid is subjected to a vulcanization process to remove most heavy metal pollutants, the waste acid enters a gypsum process to be pre-neutralized, and the concentration F of the gypsum filtrate in the buccal cavity can be controlled to be below 60-100 mg/l. And then, neutralizing the gypsum filtrate by using carbide slag, adding a flocculating agent for flocculation, and filtering to remove heavy metal pollutants in the wastewater, wherein the fluorine concentration in the flocculated filtrate can be controlled below 20-40 mg/L. Then adding aluminum sulfate solution to complex and adsorb fluoride ions, so that the concentration of F in the wastewater can be reduced to below 5mg/L, and other elements reach the standard. However, the scheme still has the problems of low reaction speed, large amount of waste residues in the reaction process and the like; as another example, chinese patent application publication No. CN101121554A, published as 2008-02-13, discloses a method for removing fluorine by integrating an electrodialysis method and an adsorption method, which is performed according to the following steps: 1. selecting a defluorinating agent with the adsorbent capacity of more than 5mg/g, installing a mechanical filter, a defluorination column tank, a precision filter and a flowmeter, communicating the defluorinating agent with a storage tank by using a pipe fitting and a stop valve, and controlling the fluorine content of water after defluorination to be 0.0-1.8 mg/L; 2. installing an electrodialyzer, a mechanical filter for pretreatment, a precision filter and a flowmeter, communicating the electrodialyzer with a storage tank by using a pipe fitting and a stop valve, and controlling the fluorine content of water after fluorine removal to be 0.0-1.8 mg/L; 3. installing a storage tank, and marking scales and water storage capacity on the tank body; 4. starting the adsorption method type and electrodialysis method type fluorine removal devices, calculating the water fluorine content of one fluorine removal method by using the water fluorine content of the other fluorine removal method, and regulating the ratio of the water fluorine content and the water fluorine content of the other fluorine removal method into a storage tank by using a flowmeter; 5. blending: for example, the fluorine content in the water is 0.2mg/L by electrodialysis method and 1.6mg/L by adsorption method at a ratio of 1: 1, and so on. The integrated defluorination method has the advantages that the water resource utilization rate is improved by times compared with that of a single defluorination method, but the water content in water is still required to be 0.0-1.8 mg/L before electrodialysis, the water quality requirement is strict, raw water needs to be pretreated, the treatment cost is improved, and the water quality of outlet water cannot meet the requirement of ultrapure water in the electronic industry.
In addition, in the current photovoltaic industry, integrated circuit industry and semiconductor industry, a large amount of ultrapure water with high water quality level is needed for washing, for example, in the process flow of semiconductor device preparation, the silicon wafer washing link accounts for 17% of the total process steps according to statistics. In the electronic industry, tap water is commonly used as raw water to prepare ultrapure water, and the extremely large demand of the ultrapure water makes the water cost of the tap water become a non-negligible part of the ultrapure water preparation cost. Therefore, if the wastewater in the electronic industry can meet the requirement of the ultrapure water preparation system on the quality of raw water, the cost for preparing ultrapure water can be greatly reduced, and the production cost of electronic products can be reduced.
The requirements of the quality of ultrapure water in the electronic and semiconductor industries in ASTM D5127-13(2018) specify that the fluorine content in water for microelectronic production equipment with a line width of 0.5-1.0 um should be controlled within 0.1 ug/L. This is because the presence of fluorine in ultrapure water can affect the quality of the product produced, as during wafer fabrication fluorine is the primary contaminant causing keymat failure, and fluorine contamination can cause corrosion and defects in the aluminum keymat, thereby affecting the quality of the microchip being fabricated. For another example, in a process flow for manufacturing an Integrated Circuit (IC), ultrapure water is mainly used for removing surface contaminants (particles) and treating a circuit board after a wet pickling process, the circuit board is subjected to 50 times of ultrapure water circulation treatment, and thus ionic impurities in water adversely affect the quality of a final product. The silicon plate atoms located on the surface of the circuit board have a large number of unsaturated bonds and therefore have very high chemical activity and corresponding adsorption properties, and the adsorbed inorganic contaminants on the surface will increase the defects of the deposited layer, which can diffuse into the bulk, resulting in structural defects. Ion contamination can cause closure between conductors, corrode conductors, cause distortion of the topological pattern of the IP layer, and the like. Therefore, when the water is discharged from the electronic wastewater treatment process, the ultrapure water preparation system can be ensured to have a certain removal effect on fluorine in the recycled water, so that the ultrapure water meets the water quality requirement of the electronic and semiconductor industry. The concentration of fluorine ions in effluent water of the defluorination process such as the precipitation method, the adsorption method, the electrochemical method, the membrane treatment method and the like which are commonly used at present is often in the mg/L level, and the requirement of ultrapure water in the electronic industry cannot be met.
Therefore, it is imperative to develop a practical defluorination process.
Disclosure of Invention
1. Problems to be solved
Aiming at the problems, the invention provides a method for treating fluorine-containing reuse water, which combines chemical precipitation, flocculation precipitation and EDI water treatment technologies, has extremely low fluorine content in effluent, can reach the standard of ultrapure water, and has high fluorine removal efficiency, high wastewater reuse rate and low operation cost.
2. Technical scheme
In order to solve the problems, the technical scheme adopted by the invention is as follows:
a method for treating fluorine-containing reuse water comprises the following steps:
(1) pretreatment: introducing excessive calcium hydroxide and calcium chloride solution into fluorine-containing wastewater with the pH value of 8-9 to generate calcium fluoride, and adjusting the pH value of inlet water;
it should be noted here that the water quality (mainly pH and fluorine content) of the wastewater needs to be detected in advance, and the "fluorine-containing wastewater with a pH value of 8 to 9" may be original wastewater that has not been adjusted by acid and alkali, or may be wastewater that has been adjusted by acid and alkali as needed; and introducing excessive calcium ions into the water body according to the detected fluorine content, wherein the excessive calcium ions are more than the theoretical requirement for completely precipitating the fluorine ions by taking the fluorine contained in the wastewater as a standard.
(2) Adding a coagulant into the pretreated wastewater, then adjusting the pH value of the wastewater to 6-7, and introducing a flocculant;
(3) filtering, namely taking supernatant from the wastewater after flocculation precipitation, filtering (removing solid impurities in the wastewater by using a cylindrical filter), and then performing reverse osmosis treatment by using reverse osmosis membrane filtration;
(4) TOC degradation and ultraviolet sterilization, wherein TOC degradation treatment is carried out on the effluent of the reverse osmosis membrane (by utilizing a TOC degradation device), and then ultraviolet irradiation treatment is carried out;
(5) EDI treatment, namely treating the wastewater by an electrodeionization system, wherein the resin filled in the electrodeionization system is porous polystyrene resin (HZO-201) loaded with nano hydrous zirconia;
(6) TOC degradation and ultraviolet sterilization, wherein the TOC degradation device is used for carrying out TOC degradation treatment on EDI effluent (185 nm ultraviolet light is adopted by the TOC degradation device and the degradation device), and then the TOC degradation treatment and the ultraviolet irradiation sterilization treatment are carried out;
(7) a precision filter: the water after the ultraviolet irradiation treatment is filtered by a precision filter (PP spray-melting type filter element with the filter element precision of 5 um).
Preferably, in the step (1), the adding mass concentration of the calcium hydroxide is based on the fluorine content in the wastewater
The adding mass concentration of the calcium chloride is
The unit of the mass concentration is mg/L, and the introduced calcium hydroxide and calcium chloride can generate chemical precipitation reaction with fluoride ions to generate calcium fluoride.
Preferably, in the step (2), the coagulant is PAC, and the adding amount is C based on the mass concentration of fluorine in the water bodyPAC＝4CF -(ii) a The flocculant is PAM, the mass concentration of fluorine in the water body is taken as a reference, and the adding amount is CPAM＝4CF -. In the step (1), a flocculating agent is added firstly, and then the pH is adjusted, so that the CaF generated in the step (1)2The precipitation effect may be enhanced by converting the precipitate into larger particles, followed by the introduction of a flocculating agent.
Preferably, in the step (4), the ultraviolet irradiation is specifically to treat the effluent after TOC degradation by using a UV-254nm ultraviolet sterilizer.
In the step (3), the supernatant of the flocculation precipitation is primarily filtered, so as to remove solid impurities in the wastewater; then, treating the wastewater by using a reverse osmosis membrane so as to remove soluble substances such as sodium, calcium, magnesium, chloride, nitrate, carbonate and the like; treating the effluent of the reverse osmosis membrane by using a TOC degradation device in the step (4), catalyzing by high-dose UV-185nm ultraviolet light to generate hydroxyl radicals in water, and oxidizing and degrading organic matters, ozone, chlorine and chloramine in the water, so as to reduce the TOC content in the water; the TOC degraded effluent can be further sterilized by using a UV-254nm ultraviolet sterilizer.
Preferably, in the step (5), the EDI treatment specifically includes first performing a first-stage EDI treatment on the effluent from the step (4) (the resin in the electrodeionization system used in the step is a gel-type strong resin) to remove the gas dissolved in the water body, boron and silicon dioxide; and then carrying out secondary EDI treatment, wherein the resin filled in the electrodeionization system of the secondary EDI treatment is porous polystyrene resin loaded with nano hydrous zirconia, so as to further improve the removal rate of fluorine. The porous polystyrene resin loaded with nano hydrous zirconia described herein (the porous polystyrene resin loaded with nano hydrous zirconia is a reference, and studies on the preparation and defluorination performance of the porous polystyrene resin loaded with nano hydrous zirconia were conducted, HZO-201 in 2014-05-28).
Preferably, in the step (5), the concentration of fluorine ions in the feed water during the secondary EDI treatment is 0-5 mg/L. In addition, other specific processing parameters are as follows: the pH value of inlet water is 5.8-8.0; the temperature is 5-35 ℃; the water inlet pressure is 1.5-4kg/cm2。
Preferably, in step (6), the TOC degradation and UV sterilization process is the same as that in step (4).
Preferably, in the step (7), the precision filter has a filtration precision of 5 um.
Ultrapure water is prepared by the method for treating the fluorine-containing reuse water.
The ultrapure water is applied to the process of manufacturing integrated circuits and cleaning circuit boards.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention provides a method for treating fluorine-containing reuse water, which is used for treating fluorine-containing wastewater (especially fluorine-containing wastewater in the electronic industry) and has the following advantages: firstly, the removal rate of fluorine ions in the wastewater is high, and the level of ultrapure water can be reached; secondly, the fluorine ion removal efficiency is high; thirdly, the recovery rate of the wastewater can be greatly improved, and the running cost of the ultrapure water preparation system is obviously reduced;
(2) the invention provides a method for treating fluorine-containing reuse water, which comprises the steps of firstly, carrying out flocculation precipitation and filtration treatment on waste water to remove CaF2Precipitating particles and other solid impurities in the wastewater to prevent the blockage of the permeable membrane in the next step; then, a reverse osmosis membrane is used for treating the wastewater, so that soluble substances such as sodium, calcium, magnesium, chloride, nitrate, carbonate and the like are removed, the hardness of a water body is reduced, and calcium and magnesium scales are prevented from influencing subsequent treatment steps; then, treating the effluent by adopting a first-level EDI technology, and removing dissolved gas, boron and silicon dioxide; followed by nano-hydration using a filling with a loadingThe secondary EDI system of the porous polystyrene resin of zirconia is used for treating the wastewater, so that the fluorine content in the water body is further reduced; finally, performing TOC secondary degradation and ultraviolet sterilization on the water body, namely performing precise filtration to ensure that the water quality of the outlet water reaches the level of ultrapure water;
(3) in a conventional ultrapure water production system, impurity ions in raw water are generally removed by an RO/EDI integration technique, but the target of the above technique is mostly tap water. However, in the present patent application, the radius of the contained fluorine ions is small, and the content of the fluorine ions in the effluent of the reverse osmosis membrane is still high, and for the conventional EDI technology, when the ion exchange resin removes the impurity ions in the wastewater by using the ion exchange principle, the fluorine ions are ranked relatively backward, so the removal effect of the fluorine ions is affected by anions such as sulfate radicals, nitrate radicals, chromate radicals, bromide ions, cyanide ions, chloride ions and the like, and the electronic wastewater contains a large amount of anions, so when the recycled electronic wastewater is used as raw water of an ultrapure water preparation system, the fluorine removal effect of the EDI technology is not ideal;
based on the above, the invention provides a method for treating fluorine-containing reuse water, which is a method for combining primary EDI treatment and secondary EDI treatment on a water body, and is used for treating fluorine-containing wastewater; in the treated secondary EDI system, the adopted resin is porous polystyrene resin loaded with nano hydrous zirconia, and the method has the following advantages: firstly, water is dissociated into hydrogen ions and hydroxide ions through polarization in an ion exchange resin and an interface diffusion layer of the ion exchange membrane in contact with water, the hydrogen ions and the hydroxide ions are used for regeneration of the resin besides loading current, and the nano hydrous zirconia loaded on the resin enhances the conductivity of the resin, so that more hydrogen ions and hydroxide ions can be used for regenerating the resin, and the regeneration rate of the resin is ensured; secondly, in the conventional EDI technique, water is dissociated under the action of an electric field to generate hydrogen ions and hydroxyl ions, and a part of the ions are dissociated for resin regeneration and the other part is used for carrying current. In the technology, the porous polystyrene resin loaded with the nano-hydrous zirconia is loaded with the nano-hydrous zirconia to enhance the conductivity of the resin, so that more hydrogen ions and hydroxyl ions generated by water electrolysis are used for resin regeneration, the removal effect of the ion exchange resin on impurity ions is improved, and the defluorination effect of the defluorination resin is enhanced;
(4) for the existing fluorine removal technology of porous polystyrene resin loaded with nano-hydrated zirconia, after fluorine removal is carried out for a period of time in the use process, a desorption agent is needed to desorb the fluorine removal resin, and the desorption regeneration of the resin can greatly increase the operation cost of the resin during fluorine removal. In order to improve the feasibility of industrial popularization of the special defluorinating resin, the technology combines electrodialysis and ion exchange resin to realize continuous regeneration of the novel defluorinating resin, saves the cost required by desorption regeneration in the use process of the resin, and greatly reduces the operation cost of the special defluorinating resin during defluorination.
Detailed Description
The invention is further described with reference to specific examples.
Example 1
In the embodiment, 2L of fluorine-containing wastewater in the electronic industry is taken from a microelectronic manufacturing plant, the pH value of raw water is 2.84, the COD concentration is 86mg/L, and the fluorine ion concentration is 364mg/L (the fluorine ion concentration in the wastewater is measured by using a direct ion selective electrode method, the lower detection limit is 15.1 mug/L), and the wastewater is treated by using the treatment method provided by the invention, and the specific steps are as follows:
(1) and adjusting the pH value of the wastewater to 8-9, and introducing an excessive calcium hydroxide solution and a calcium chloride solution into the wastewater to perform a chemical precipitation reaction to generate calcium fluoride.
(2) Flocculating and precipitating, namely (1) introducing a coagulant PAC into the wastewater after a chemical precipitation reaction to enable fine precipitates to generate larger particles, then adjusting the pH of the wastewater to 6-7, and then introducing a flocculant PAM to enhance the precipitation effect.
(3) And (3) taking the supernatant in the step (2), removing solid impurities in the wastewater by using a cylindrical filter, and removing soluble substances such as sodium, calcium, magnesium, chloride, nitrate, carbonate and the like from the wastewater by using a reverse osmosis membrane.
(4) TOC degradation and ultraviolet sterilization, wherein TOC degradation treatment is carried out on the effluent of the reverse osmosis membrane (by utilizing a TOC degradation device), and then ultraviolet irradiation treatment is carried out, so that hydroxyl free radicals can be generated in water through high-dose UV-185nm ultraviolet catalysis, and organic matters in the water are subjected to oxidative degradation, so that the TOC content in the water is reduced;
and (4) treating the effluent after TOC degradation by using a UV-254nm ultraviolet sterilizer.
(5) EDI treatment, namely treating the effluent in the step (4) by using an electrodeionization system, wherein the resin filled in the electrodeionization system is porous polystyrene resin loaded with nano hydrous zirconia; the specific processing parameters are as follows: the pH value of inlet water is 5.8-8.0; the temperature is 5-35 ℃; the water inlet pressure is 1.5-4kg/cm2。
The water quality of the wastewater after EDI treatment is shown in Table 1:
TABLE 1 EDI quality of treated wastewater
(6) TOC degradation and ultraviolet sterilization, performing TOC degradation treatment on EDI effluent (by using a TOC degradation device), and sterilizing by using an UV-254nm ultraviolet sterilizer.
(7) A precision filter: the water after the ultraviolet irradiation treatment is filtered by a precision filter (PP spray-melting type filter element with the filter element precision of 5 um).
The total effluent quality is shown in table 2:
TABLE 2 Total effluent quality
In the table, "-" indicates that the fluorine ion concentration in the water body is lower than the lower detection limit of 15.1. mu.g/L.
As can be seen from the data in tables 1 and 2, after the wastewater is treated by the newly developed defluorination technology, the removal rate of the fluoride ions in the wastewater reaches 95%, the wastewater is further subjected to advanced treatment by a TOC degrader, a polishing mixed bed, an ultraviolet sterilizer and a precision filter, the existence of the fluoride ions is not detected by using a direct ion selective electrode method, the removal rate of the fluoride ions in the whole process reaches more than 99%, and the quality of effluent meets the requirement of ultrapure water in the electronic industry.
Example 2
In the embodiment, 2L of fluorine-containing wastewater in the electronic industry is taken from a microelectronic manufacturing plant, the pH value of raw water is 2.84, the COD concentration is 86mg/L, and the fluorine ion concentration is 364mg/L (the fluorine ion concentration in the wastewater is measured by using a direct ion selective electrode method, the lower detection limit is 15.1 mug/L), and the wastewater is treated by using the treatment method provided by the invention, and the specific steps are as follows:
(1) adjusting the pH value of the wastewater to 8-9, and introducing an excessive calcium hydroxide solution and a calcium chloride solution into the wastewater to perform a chemical precipitation reaction to generate calcium fluoride; the mass concentration of fluorine in the water body is taken as a reference, and the adding amount of the calcium hydroxide is
The dosage of the calcium chloride is
(2) Flocculating and precipitating, namely (1) introducing a coagulant PAC into the wastewater subjected to the chemical precipitation reaction to enable fine precipitates to generate larger particles, then adjusting the pH of the wastewater to 6-7, and then introducing a flocculant PAM to enhance the precipitation effect; the coagulant is PAC, the mass concentration of fluorine in the water body is taken as a reference, and the adding amount is CPAC＝4CF -(ii) a The flocculant is PAM, the mass concentration of fluorine in the water body is taken as a reference, and the adding amount is CPAM＝4CF -. After the treatment, the pH of the effluent was 7.96, the COD was 41mg/L, and the fluoride ion concentration was 3.2 mg/L.
(3) And (3) taking the supernatant in the step (2), removing solid impurities in the wastewater by using a cylindrical filter, and removing soluble substances such as sodium, calcium, magnesium, chloride, nitrate, carbonate and the like from the wastewater by using a reverse osmosis membrane.
(4) Treating the effluent of the reverse osmosis membrane by using a TOC degradation device (UV-185nm low-pressure high-energy ultraviolet technology), and then generating hydroxyl radicals in water by using high-dose UV-185nm ultraviolet catalysis in combination with a UV-254nm ultraviolet sterilizer so as to oxidize and degrade organic matters in the water to reduce the TOC content in the water;
then sterilizing with UV-254nm ultraviolet sterilizer.
(5) EDI treatment, namely performing primary EDI treatment on the effluent obtained in the step (4) by using an electrodeionization system filled with gel type strong resin; the specific processing parameters are as follows: the pH value of inlet water is 5.8-8.0; the temperature is 5-35 ℃; the water inlet pressure is 1.5-4kg/cm2；
Then, an electrodeionization system filled with porous polystyrene resin loaded with nano hydrous zirconia is used for carrying out secondary EDI treatment on the wastewater, and the specific treatment parameters are as follows: the pH value of inlet water is 5.8-8.0; the temperature is 5-35 ℃; the water inlet pressure is 1.5-4kg/cm2. The water quality of the wastewater after EDI treatment is shown in Table 3:
TABLE 3 EDI quality of treated wastewater
(6) And (3) disinfecting the EDI treated wastewater by a secondary TOC degradation device, a polishing mixed bed and a UV-254nm ultraviolet sterilizer.
(7) A precision filter: the water after the ultraviolet irradiation treatment was filtered with a precision filter (using a PP spray-melt filter element with a filter element precision of 5um) to prepare high resistivity electronic grade ultrapure water, and the effluent quality is shown in table 4:
TABLE 4 Total effluent quality
In the table, "-" indicates that the fluorine ion concentration in the water body is lower than the lower detection limit of 15.1. mu.g/L.
As can be seen from the data in tables 3 and 4, after the wastewater is treated by the newly developed defluorination technology, the removal rate of the fluoride ions in the wastewater reaches 95%, the wastewater is further subjected to advanced treatment by a TOC degrader, a polishing mixed bed, an ultraviolet sterilizer, a 0.1um cylindrical filter and an ultrafiltration assembly, the existence of the fluoride ions is not detected by using a direct ion selective electrode method, the removal rate of the fluoride ions in the whole process reaches more than 99%, and the quality of effluent meets the requirement of ultrapure water in the electronic industry.
Example 3
In the embodiment, 2L of fluorine-containing wastewater in the electronic industry is taken from a microelectronic manufacturing plant, the pH value of raw water is 2.84, the COD concentration is 86mg/L, and the fluorine ion concentration is 364mg/L (the fluorine ion concentration in the wastewater is measured by using a direct ion selective electrode method, the lower detection limit is 15.1 mug/L), and the wastewater is treated by using the treatment method provided by the invention, and the specific steps are as follows:
(1) adjusting the pH value of the wastewater to 8-9, and introducing an excessive calcium hydroxide solution and a calcium chloride solution into the wastewater to perform a chemical precipitation reaction to generate calcium fluoride; the mass concentration of fluorine in the water body is taken as a reference, and the adding amount of the calcium hydroxide is
The dosage of the calcium chloride is
(2) Flocculating and precipitating, namely (1) introducing a coagulant PAC into the wastewater after a chemical precipitation reaction to enable fine precipitates to generate larger particles, then adjusting the pH of the wastewater to 6-7, and then introducing a flocculant PAM to enhance the precipitation effect.
(3) And (3) taking the supernatant in the step (2), removing solid impurities in the wastewater by using a cylindrical filter, and removing soluble substances such as sodium, calcium, magnesium, chloride, nitrate, carbonate and the like from the wastewater by using a reverse osmosis membrane.
(4) TOC degradation and ultraviolet sterilization, wherein TOC degradation treatment is carried out on the effluent of the reverse osmosis membrane (by utilizing a TOC degradation device), and then ultraviolet irradiation treatment is carried out, so that hydroxyl free radicals can be generated in water through high-dose UV-185nm ultraviolet catalysis, and organic matters in the water are subjected to oxidative degradation, so that the TOC content in the water is reduced;
and (4) treating the effluent after TOC degradation by using a UV-254nm ultraviolet sterilizer.
(5) EDI treatment, namely treating the effluent in the step (4) by using an electrodeionization system, wherein the resin filled in the electrodeionization system is porous polystyrene resin loaded with nano hydrous zirconia; the specific processing parameters are as follows: the pH value of inlet water is 5.8-8.0; the temperature is 5-35 ℃; the water inlet pressure is 1.5-4kg/cm2。
(6) TOC degradation and ultraviolet sterilization, performing TOC degradation treatment on EDI effluent (by using a TOC degradation device), and sterilizing by using an UV-254nm ultraviolet sterilizer.
(7) A precision filter: the water after the ultraviolet irradiation treatment is filtered by a precision filter (PP spray-melting type filter element with the filter element precision of 5 um).
After treatment, the existence of fluorine ions is not detected by using a direct ion selective electrode method, the removal rate of the fluorine ions in the whole process reaches over 95 percent, and the water quality of effluent meets the requirement of ultrapure water in the electronic industry.
Example 4
In the embodiment, 2L of fluorine-containing wastewater in the electronic industry is taken from a microelectronic manufacturing plant, the pH value of raw water is 2.84, the COD concentration is 86mg/L, and the fluorine ion concentration is 364mg/L (the fluorine ion concentration in the wastewater is measured by using a direct ion selective electrode method, the lower detection limit is 15.1 mug/L), and the wastewater is treated by using the treatment method provided by the invention, and the specific steps are as follows:
(1) and adjusting the pH value of the wastewater to 8-9, and introducing an excessive calcium hydroxide solution and a calcium chloride solution into the wastewater to perform a chemical precipitation reaction to generate calcium fluoride.
(2) Flocculating and precipitating, namely (1) introducing a coagulant PAC into the wastewater subjected to the chemical precipitation reaction to enable fine precipitates to generate larger particles, then adjusting the pH of the wastewater to 6-7, and then introducing a flocculant PAM to enhance the precipitation effect; the coagulant is PAC, the mass concentration of fluorine in the water body is taken as a reference, and the adding amount is CPAC＝4CF -(ii) a The flocculant is PAM, the mass concentration of fluorine in the water body is taken as a reference, and the adding amount is CPAM＝4CF -。
(3) And (3) taking the supernatant in the step (2), removing solid impurities in the wastewater by using a cylindrical filter, and removing soluble substances such as sodium, calcium, magnesium, chloride, nitrate, carbonate and the like from the wastewater by using a reverse osmosis membrane.
(4) TOC degradation and ultraviolet sterilization, wherein TOC degradation treatment is carried out on the effluent of the reverse osmosis membrane (by utilizing a TOC degradation device), and then ultraviolet irradiation treatment is carried out, so that hydroxyl free radicals can be generated in water through high-dose UV-185nm ultraviolet catalysis, and organic matters in the water are subjected to oxidative degradation, so that the TOC content in the water is reduced;
and (4) treating the effluent after TOC degradation by using a UV-254nm ultraviolet sterilizer.
(5) EDI treatment, namely treating the effluent in the step (4) by using an electrodeionization system, wherein the resin filled in the electrodeionization system is porous polystyrene resin loaded with nano hydrous zirconia; the specific processing parameters are as follows: the pH value of inlet water is 5.8-8.0; the temperature is 5-35 ℃; the water inlet pressure is 1.5-4kg/cm2。
(6) TOC degradation and ultraviolet sterilization, performing TOC degradation treatment on EDI effluent (by using a TOC degradation device), and sterilizing by using an UV-254nm ultraviolet sterilizer.
(7) A precision filter: the water after the ultraviolet irradiation treatment is filtered by a precision filter (PP spray-melting type filter element with the filter element precision of 5 um).
After treatment, the existence of fluorine ions is not detected by using a direct ion selective electrode method, the removal rate of the fluorine ions in the whole process reaches over 95 percent, and the water quality of effluent meets the requirement of ultrapure water in the electronic industry.
Comparative example 1
This comparative example differs substantially from example 2 only in that:
the first EDI treatment in step (5) is the same as the electrodeionization system of the second EDI treatment (i.e., the filled resins are all gel type strong resins)
The water quality of the wastewater after EDI treatment is shown in Table 5:
TABLE 5 quality of wastewater after EDI treatment
TABLE 6 Total effluent quality
As can be seen from the data in tables 5 and 6, after the reclaimed fluorine-containing wastewater is treated by the conventional EDI technology, the removal rate of the fluorine ions in the wastewater is 23%, and the effluent quality can not meet the requirement of ultrapure water in the electronic industry after the wastewater is further subjected to advanced treatment by a TOC degradation device, a polishing mixed bed, an ultraviolet sterilizer, a 0.1um cylindrical filter and an ultrafiltration assembly. Therefore, if the fluorine-containing wastewater after the primary fluorine removal treatment is reused as raw water of an ultrapure water system, ultrapure water meeting the industrial production requirements cannot be prepared by using an ultrapure water preparation system composed of a conventional EDI device, so that the ultrapure water preparation system needs to be further improved when the fluorine-containing wastewater is recycled.
Comparative example 2
This comparative example differs substantially from example 2 only in that:
in the step (5), the EDI treatment technology is replaced by an electrodialysis treatment method.
The basic conditions are as follows: assembling three stages of membranes by adopting a die type clapboard electrodialyzer 400 x 800mm and 150 pairs of membranes;
polyethylene heterogeneous membranes are selected.
TABLE 7 Water quality before and after electrodialysis treatment
TABLE 8 Total effluent quality
It can be seen from the data in tables 7 and 8 that, after the recycled fluorine-containing wastewater is treated by the conventional electrodialysis technology, the removal rate of the fluoride ions in the wastewater is only 14%, even if the wastewater is further subjected to advanced treatment by a TOC degrader, a polishing mixed bed, an ultraviolet sterilizer, a 0.1um cylindrical filter and an ultrafiltration module, the content of the fluoride ions is still high, and the quality of the effluent water does not meet the requirement of ultrapure water in the electronic industry. Therefore, if the fluorine-containing wastewater after the preliminary fluorine removal treatment is reused as raw water of an ultrapure water system, ultrapure water satisfying industrial production requirements cannot be prepared by using an ultrapure water preparation system composed of a conventional electrodialysis device.
Claims (8)
1. A method for treating fluorine-containing reuse water is characterized by comprising the following steps:
(1) pretreating, namely introducing excessive calcium hydroxide and calcium chloride into fluorine-containing wastewater with the pH value of 8-9;
(2) flocculating and precipitating, namely adding a coagulant into the pretreated water body, then adjusting the pH value of the wastewater to 6-7, and then introducing a flocculating agent;
(3) filtering, namely taking supernatant from the wastewater after flocculation and precipitation, filtering, and then performing reverse osmosis treatment by using a reverse osmosis membrane;
(4) TOC degradation and ultraviolet sterilization, namely performing TOC degradation and ultraviolet irradiation sterilization treatment on the effluent of the reverse osmosis membrane;
(5) EDI treatment, namely treating the water body subjected to ultraviolet irradiation sterilization treatment by using an electrodeionization system, wherein the resin filled in the electrodeionization system is porous polystyrene resin loaded with nano hydrous zirconia;
(6) TOC degradation and ultraviolet sterilization, namely performing TOC degradation treatment on EDI effluent, and performing ultraviolet irradiation sterilization treatment;
(7) performing precision filtration, namely filtering the water body after ultraviolet irradiation treatment by using a precision filter;
in the step (5), the EDI treatment is specifically that the effluent water obtained in the step (4) is subjected to first-stage EDI treatment and then to second-stage EDI treatment, wherein the resin filled in the electrodeionization system of the second-stage EDI treatment is porous polystyrene resin loaded with nano hydrous zirconia;
during the second-stage EDI treatment, the fluorine ions in the inlet water are concentratedThe degree is 0-5 mg/L; the specific processing parameters are as follows: the pH value of inlet water is 5.8-8.0; the temperature is 5-35 ℃; the water inlet pressure is 1.5-4kg/cm2。
2. The method for treating fluorine-containing reuse water according to claim 1, wherein in the step (1), the calcium hydroxide is added in an amount of about equal to the mass concentration of fluorine in the water body
The dosage of the calcium chloride is
3. The method according to claim 1, wherein in the step (2), the coagulant is PAC, and the addition amount thereof is C based on the mass concentration of fluorine in the water bodyPAC＝4CF -(ii) a The flocculant is PAM, the mass concentration of fluorine in the water body is taken as a reference, and the adding amount is CPAM＝4CF -。
4. The method for treating fluorine-containing reuse water according to claim 1, wherein in the step (4), the ultraviolet irradiation is performed by treating the effluent after TOC degradation with a UV-254nm ultraviolet sterilizer.
5. The method for treating fluorine-containing reuse water according to claim 4, wherein in the step (5), the upper limit of the concentration of fluorine ions in the feed water of the secondary EDI treatment is 5 mg/L.
6. The method for treating fluorine-containing reuse water according to claim 1, wherein in the step (7), the filtration precision of the precision filter is 5 μm.
7. Ultrapure water, which is produced by the method for treating fluorine-containing reuse water according to any one of claims 1 to 6.
8. Use of ultrapure water according to claim 7 for the cleaning of circuit boards in processes for the manufacture of integrated circuits.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910815633.0A CN110451704B (en) | 2019-08-30 | 2019-08-30 | Method for treating fluorine-containing reuse water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910815633.0A CN110451704B (en) | 2019-08-30 | 2019-08-30 | Method for treating fluorine-containing reuse water |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110451704A CN110451704A (en) | 2019-11-15 |
| CN110451704B true CN110451704B (en) | 2020-09-11 |
Family
ID=68490099
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910815633.0A Active CN110451704B (en) | 2019-08-30 | 2019-08-30 | Method for treating fluorine-containing reuse water |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110451704B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113003754A (en) * | 2019-12-18 | 2021-06-22 | 松栢投资有限公司 | Water inlet flow control device and method for waste liquid recycling and regeneration |
| CN113087040B (en) * | 2021-04-20 | 2022-10-14 | 山西国际电力技术咨询有限公司 | Novel defluorinating agent and fluorine-containing waste liquid treatment process |
| JP2023037938A (en) * | 2021-09-06 | 2023-03-16 | オルガノ株式会社 | Water treatment method and apparatus |
| CN113788558A (en) * | 2021-09-08 | 2021-12-14 | 武汉工程大学 | Method for removing fluorine in phosphogypsum leachate by using reverse osmosis membrane |
| CN114291959B (en) * | 2022-03-09 | 2022-07-01 | 中国电子工程设计院有限公司 | Preparation method of ultrapure water capable of effectively removing total organic carbon and weakly ionized impurities |
| CN114656099A (en) * | 2022-03-25 | 2022-06-24 | 东莞东元环境科技股份有限公司 | Method and system for recovering fluorine-containing wastewater |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7470366B2 (en) * | 2004-05-07 | 2008-12-30 | Ge Mobile Water, Inc. | Water purification system and method using reverse osmosis reject stream in an electrodeionization unit |
| CN103030234A (en) * | 2011-10-10 | 2013-04-10 | 浙江科技学院 | Method for treating fluoride wastewater in integrated circuit industry |
| CN102942239B (en) * | 2012-12-10 | 2014-04-09 | 南京大学 | Preparation method of composite material |
| WO2016028972A1 (en) * | 2014-08-20 | 2016-02-25 | Evoqua Water Technologies Llc | Water treatment system and method |
| CN105347553B (en) * | 2015-11-17 | 2018-07-13 | 南京麦得文环保科技有限公司 | A kind of LED industry chip production waste water treatment system and processing method |
| CN206255944U (en) * | 2016-12-16 | 2017-06-16 | 东莞市秦泰盛实业有限公司 | A kind of 12 tons of ultra-pure water EDI systems per hour |
| CN207567042U (en) * | 2017-12-06 | 2018-07-03 | 杭州真水流体技术有限公司 | A kind of ultra-pure-water treatment system |
| CN109775904A (en) * | 2019-03-05 | 2019-05-21 | 北京赛科康仑环保科技有限公司 | A kind of processing method preparing electronic grade ultrapure water using LED industry waste water containing As |
-
2019
- 2019-08-30 CN CN201910815633.0A patent/CN110451704B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN110451704A (en) | 2019-11-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110451704B (en) | Method for treating fluorine-containing reuse water | |
| JP3426072B2 (en) | Ultrapure water production equipment | |
| KR100784438B1 (en) | apparatus and method for continuous electrodeionization | |
| TWI648093B (en) | Ultrapure water manufacturing device and method | |
| CN1176032C (en) | Producing process and technology for electronic grade water by intergrated film process | |
| WO2005095280A1 (en) | Apparatus for producing ultrapure water | |
| CN113003846B (en) | Zero-emission treatment process and system for sewage with high salt content and high COD (chemical oxygen demand) | |
| WO2015012054A1 (en) | Method and device for treating boron-containing water | |
| CN104108813B (en) | Refinery sewage desalination integrated processing technique and device | |
| CN111252971A (en) | Ultrapure water manufacturing system and ultrapure water manufacturing method using same | |
| CN110683709A (en) | Zero-discharge treatment method for fluorine-containing wastewater | |
| TWI540103B (en) | Method for removing boron from a boron-containing wastewater | |
| CN103787525A (en) | Two-stage biochemical effluent in-depth treatment method for municipal sewage | |
| CN216998076U (en) | Industrial wastewater treatment system | |
| JP6228471B2 (en) | To-be-treated water processing apparatus, pure water production apparatus and to-be-treated water processing method | |
| WO2018096700A1 (en) | System for producing ultrapure water and method for producing ultrapure water | |
| CN113003845B (en) | Zero-emission treatment process and system for sewage with high sulfate content and high COD (chemical oxygen demand) | |
| CN105217846B (en) | Cold rolling alkalescence waste discharge advanced treatment system and processing method | |
| MX2010012427A (en) | Apparatus for treating wastewater, particularly wastewater originating from a process for the production of photovoltaic cells. | |
| CN111777244A (en) | Ultrapure water preparation system and preparation process thereof | |
| JP2017127875A (en) | Ultrapure water system and ultrapure water production method | |
| CN206624737U (en) | A kind of organic wastewater reverse osmosis concentrated water oxidation and desalination system | |
| CN106396244A (en) | A waste water treating system suitable for an electronic factory | |
| KR100314714B1 (en) | System of manufactured for ultra pure water | |
| CN115925141A (en) | Deep fluorine removal process for fluorine-containing wastewater |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |