CN107176726A - Desulphurization for Coal-fired Power Plant waste water integrates defluorination method - Google Patents
Desulphurization for Coal-fired Power Plant waste water integrates defluorination method Download PDFInfo
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- CN107176726A CN107176726A CN201710459510.9A CN201710459510A CN107176726A CN 107176726 A CN107176726 A CN 107176726A CN 201710459510 A CN201710459510 A CN 201710459510A CN 107176726 A CN107176726 A CN 107176726A
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- Prior art keywords
- desulfurization wastewater
- waste water
- water
- defluorination
- coal
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title claims abstract description 54
- 238000006115 defluorination reaction Methods 0.000 title claims abstract description 25
- 239000010908 plant waste Substances 0.000 title claims abstract description 11
- 239000002351 wastewater Substances 0.000 claims abstract description 86
- 239000010802 sludge Substances 0.000 claims abstract description 43
- 238000005345 coagulation Methods 0.000 claims abstract description 36
- 230000015271 coagulation Effects 0.000 claims abstract description 36
- 238000012545 processing Methods 0.000 claims abstract description 24
- 230000008569 process Effects 0.000 claims abstract description 21
- 238000004062 sedimentation Methods 0.000 claims abstract description 21
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000005516 engineering process Methods 0.000 claims abstract description 19
- 238000001179 sorption measurement Methods 0.000 claims abstract description 14
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 12
- 230000008859 change Effects 0.000 claims abstract description 12
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 8
- 231100000719 pollutant Toxicity 0.000 claims abstract description 8
- 238000002161 passivation Methods 0.000 claims abstract description 7
- 230000010287 polarization Effects 0.000 claims abstract description 6
- 230000003311 flocculating effect Effects 0.000 claims abstract description 5
- 238000006477 desulfuration reaction Methods 0.000 claims description 72
- 230000023556 desulfurization Effects 0.000 claims description 71
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 60
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 238000005189 flocculation Methods 0.000 claims description 16
- 230000016615 flocculation Effects 0.000 claims description 16
- 238000005868 electrolysis reaction Methods 0.000 claims description 15
- 229920000642 polymer Polymers 0.000 claims description 14
- 238000011282 treatment Methods 0.000 claims description 14
- 239000006228 supernatant Substances 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 238000010521 absorption reaction Methods 0.000 claims description 11
- 150000002500 ions Chemical class 0.000 claims description 11
- 230000033228 biological regulation Effects 0.000 claims description 10
- 238000001556 precipitation Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 239000004411 aluminium Substances 0.000 claims description 9
- 238000004061 bleaching Methods 0.000 claims description 9
- 239000002244 precipitate Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000012530 fluid Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000013049 sediment Substances 0.000 claims description 5
- 230000007246 mechanism Effects 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- 239000000701 coagulant Substances 0.000 claims description 3
- 239000000084 colloidal system Substances 0.000 claims description 3
- 239000000356 contaminant Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 2
- 230000006641 stabilisation Effects 0.000 claims 1
- 238000011105 stabilization Methods 0.000 claims 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 25
- 229910052731 fluorine Inorganic materials 0.000 abstract description 25
- 239000011737 fluorine Substances 0.000 abstract description 25
- 238000004065 wastewater treatment Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- 238000009297 electrocoagulation Methods 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 3
- 230000000593 degrading effect Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000007667 floating Methods 0.000 abstract description 3
- 230000002265 prevention Effects 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 230000010354 integration Effects 0.000 abstract description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 18
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 15
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- 230000005611 electricity Effects 0.000 description 7
- 230000001105 regulatory effect Effects 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 6
- 229910001385 heavy metal Inorganic materials 0.000 description 6
- 238000003672 processing method Methods 0.000 description 6
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 239000005864 Sulphur Substances 0.000 description 5
- 235000011941 Tilia x europaea Nutrition 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000004571 lime Substances 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000003546 flue gas Substances 0.000 description 4
- 229910001425 magnesium ion Inorganic materials 0.000 description 4
- 229940070527 tourmaline Drugs 0.000 description 4
- 229910052613 tourmaline Inorganic materials 0.000 description 4
- 239000011032 tourmaline Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 239000012267 brine Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 241000370738 Chlorion Species 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- ZGBSOTLWHZQNLH-UHFFFAOYSA-N [Mg].S(O)(O)(=O)=O Chemical compound [Mg].S(O)(O)(=O)=O ZGBSOTLWHZQNLH-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- -1 colourity Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000002940 repellent Effects 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 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 1
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000005276 aerator Methods 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229940000489 arsenate Drugs 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000502 dialysis 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
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000004334 fluoridation Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000009287 sand filtration Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000010801 sewage sludge Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/463—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrocoagulation
-
- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F2001/007—Processes including a sedimentation step
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/18—Nature of the water, waste water, sewage or sludge to be treated from the purification of gaseous effluents
-
- 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 Of Suspended Particles By Flocculating Agents (AREA)
- Removal Of Specific Substances (AREA)
Abstract
Desulphurization for Coal-fired Power Plant waste water integrates defluorination method, overcritical electric coagulation, the mixed inclined plate sedimentation of change and Defluorination of Formation Mater By Adsorption On Activated Alumina are adsorbed into the mutually coordinated support integration of three kinds of technologies to be integrated, overcome prior art defect, the fluorine-containing sludge settleability obtained in wastewater treatment process is good, dewatering is good and sludge quantity greatly reduces, and realizes fluorine-containing sludge minimizing.On the basis of electrolytic cell progress Wastewater by Electric flocculating principles, merge high-frequency impulse technology, make equipment during waste water is handled while having the effect of the multiple degradings such as electrocoagulation, electric floating and electrochemical redox, substantially increase the clearance of pollutant, concentration polarization and prevention electrode passivation problem are reduced simultaneously, and notable extension electrode life simultaneously improves electric current conduction efficiency.Processing procedure simple and effective, operating automation degree is high.System run all right is reliable, and energy consumption is low, and operating cost is low, and substantially reduces processing time, good environmental protection, it is ensured that water outlet reaches discharge standard, and can save a large amount of medicaments.
Description
Technical field
The present invention relates to the processing improved technology of C02F water, waste water, sewage or sludge, especially Desulphurization for Coal-fired Power Plant waste water
Comprehensive defluorination method.
Background technology
Coal-burning power plant can produce substantial amounts of oxysulfide (SOx), such as sulfur dioxide during coal fired power generation is used
(SO2), in order to remove the sulfur dioxide in flue gas, coal-burning power plant can use exhaust gas desulfurization (FGD, Flue Gas
Desulfurization) equipment, is carried out by a large amount of divalent alkaline-earth metal industrial waters are extracted with the sulphur-containing exhaust gas in flue gas
Desulphurization reaction, then will be given up by " desulfurization " the reacted acid waste water processing discharge containing sulfate radical, hereinafter referred to as desulfurization
Water.The composition of the desulfurization wastewater, 20000mg/L, i.e. 20000ppm sulfate ion are more than containing concentration, and concentration is more than
600ppm chlorion, fluorine ion and concentration of the concentration between 50~200ppm is outstanding between 1000~4000ppm
Floating solid (Suspended Solid), hereinafter referred to as SS compositions, additionally containing a large amount of metal magnesium ions.
In recent years, national governments are increasingly severe for the requirement of environmental standard, water standard, China《Composite wastewater is discharged
Standard》Regulation, for the discharge water of the fluorine ion containing 50~200ppm, hereinafter referred to as fluoride waste, also requiring that needs height
Purification is down to below 10ppm to content of fluoride ion, can just be discharged into sea.
Technology of Fluoride Removal mainly includes absorption method, ion-exchange, electrochemical process and chemical method etc. both at home and abroad at present.Absorption method
Technology of Fluoride Removal is typically only used for drinking water defluorination of the Oil repellent less than 10mg/L and handled, and cost is high, is not suitable for flood
Measure industrial wastewater fluorine removal field；Ion-exchange is the exchange capacity using ion exchange resin, goes one of fluorine ion in water removal
Kind of method, compound resin fluoride removing rate is high, can regenerate, and removal efficiency can be reduced by being disadvantageous in that in the presence of other anion,
Resin regeneration can cause fluorine concentrate discarded object, it is necessary to be acted upon abandoning again；Electrochemical process includes electrocoagulation and electricity
Dialysis, electrocoagulation need to be operated through separation of solid and liquid, and the shortcoming that the water discharge of enriched chamber is polluted in electroosmose process is also limited
The practical application of electrochemical process；Chemical precipitation method technology of Fluoride Removal is one of technique conventional in engineering, as shown in Figure 1, is taken off
Sulphur waste water converges with bleaching water sequentially enters mixed groove and stillpot slowly behind repeated pond respectively and jogging groove, excluded by stillpot
Precipitating sludge is into extruder processing, and shunting treatment fluid, which is introduced, releases outer row behind pond.The technique is applied in high fluorine wastewater treatment
More, the method for wherein feeding lime is that a kind of cost is relatively low, widely used defluorination method, but this method has some not
Foot part, for example due to lime itself the characteristics of, cause that lime utilization rate is low, chemical feeding quantity big, water outlet fluorine ion is difficult to be removed to
Reduced levels；Coagulation sedimentation is also conventional defluorinating process, for desulfurization wastewater, and traditional coagulant precipitation method is addition sulphur
Sour aluminium or liquid caustic soda, but a large amount of grease states, the sludge of settleability difference can be formed, such a moisture percentage in sewage sludge is high, separation of solid and liquid is stranded
Difficulty, and generate the tiny particulate matter of many particle diameters, pollutes that thing outlet effect is not good, and sludge is difficult to reuse and stores up occupation of land
Big the problems such as, form secondary solid waste pollution.On the other hand, because the fluorine element overwhelming majority in wastewater treatment is finally all entered
Enter into sludge, therefore the Oil repellent in sludge is higher, in storage, transport and disposal process, it is easy to cause more serious
With extensive secondary pollution, and this pollution to soil and groundwater once formed, recover difficulty it is very big.
The related art scheme of solution above technical problem discloses less.
Chinese patent application 201610301503.1 provides a kind of desulfuration waste water treatment process, comprises the following steps：1)
Water quality adjustment groove；2) precipitation tank in term；3) stillpot；4) fluorine removal reactive tank；5) defecator；6) neutralization chamber；7) film process list
Member；8) letdown tank.Effective reducing substances (COD), Cr VI, fluorine ion eliminated in waste water etc..It is useless with certain power plant desulfurization
Exemplified by water process, it is less than 100mg/L, six by neutralizing effluent index COD in the integrated use of the techniques such as reduction, actual motion
Valency chromium is less than 10mg/L less than 0.5mg/L, fluorine ion.
Chinese patent application 201610025645.X discloses a kind of method for treating desulfurized wastewater, step 1) desulfurization wastewater entrance
In aerating regulation pond, under aerator effect, the sulfite ion in desulfurization wastewater is oxidized to sulfate ion；Step
Rapid 2) to be then sent to pH regulating boxs, the feeding lime into pH regulating boxs is removed temporarily hard；Step 3) in first order reaction flow tank
In, further precipitate the heavy metal that can not be precipitated out with hydroxide form by adding organic sulfur；Step 4) it is being divided into two
In lattice one-level flocculation tanks, coagulant is added, cohesion forms many small flocculates；Step 5) input one-level depositing reservoir is used for pair
The suspension of itself carries out precipitation separation in the flocculate and waste water of generation；Step 6) soda ash is added in second order reaction flow tank
And sodium hydroxide solution, precipitate the calcium ion and remaining magnesium ion in waste water；Two grades of depositing reservoirs are used for the flocculate to generation
Carry out precipitation separation；More medium filter produces water by spiral atomizer, sprays into flue vaporization.
There is provided utilize nano-tourmaline for a kind of power plant desulfurization wastewater processing method of Chinese patent application 201410067893.1
A kind of power plant desulfurization wastewater processing method of haydite electric flocculation light electrolysis ultrasonic wave filter tank membrane reactor.Power plant desulfurization wastewater is entered
Enter raw water regulating reservoir stabilizing water quantity and water quality；The water outlet of raw water regulating reservoir is passed through into nano-tourmaline haydite electric flocculation light electrolysis
Ultrasonic wave filter tank removes suspended solid and impurity, and decomposable asymmetric choice net chemical substance is decomposed；Nano-tourmaline haydite electric flocculation is micro-
Electrolysis ultrasonic wave filter tank water outlet enters film filtering reactor；Recoil in nano-tourmaline haydite electric flocculation light electrolysis ultrasonic wave filter tank
Wash water is back to raw water regulating reservoir；Film filtering reactor water outlet enters charcoal canister and adsorbs residual impurity and colourity, charcoal canister
Water outlet carries out reuse.Chemical agent need not be added, electric energy is only consumed, its processing cost is greatly lowered in non-secondary pollution,
Desulfurization wastewater can reach reclaimed water reuse standard after processing, and producing water ratio is high.
Chinese patent application 201510483875.6 discloses a kind of processing method and system of wet-type magnesium method desulfurization waste water, main
To be designed to improve desulfurization wastewater treatment effect.At least include carrying out the desulfurization wastewater Air Exposure regulation desulfurization
The pH value of waste water is 10, and ammonia nitrogen is removed to adding phosphate, zeolite powder in the desulfurization wastewater, to being thrown in the desulfurization wastewater
Plus lime, molysite remove organic matter, colourity, phosphate, fluoride, the heavy metal that coal combustion is produced, regulation desulfurization wastewater PH
To 7.The clearance of the COD in desulfurization wastewater is set to bring up to more than 95%, ammonia nitrogen removal frank to more than 90.
Chinese patent application 201210367061.2 is related to the multistep treatment field of waste water, is specially that one kind is used for wet method cigarette
The useless water purifying means of desulfurization and its application method.A kind of purifier for wet flue gas desulfurization waste water, including waste water
Regulating tank (1), in addition to reaction flocculation tank (2), sedimentation basin (31), one-level fluorine removal reactive tank (41), two grades of fluorine removal reactive tanks
(42) etc..Carry out successively as follows：A. water quality and quantity is adjusted；b.Cr6+Reduction and the reaction of heavy metal ion are flocculated；c.
One-level is precipitated；D. fluorine removal is reacted and COD degradation；E. two-stage precipitation；F. neutralization reaction；G. sand filtration is handled；H. draining.
Chinese patent application 201310555063.9 is related to desulfurization wastewater " zero-emission " processing method, utilizes reverse osmosis concentrated salt
Dosing, the concentration of sediment film in water pretreatment process are combined with seawater film and anti-pollution high-pressure membrane, by containing that high-pressure membrane comes out
The strong brine of salt amount about 15~20% and the flyash reactive crystallization of grey field, form the desulfurization wastewater " zero-emission " of complete set
Handling process system, not only makes the foreign ions such as suspension, heavy metal, fluorine in desulfurization wastewater in the form of precipitating pollutant
Removing, and can reach the production water of 78%~90% rate of recovery, other ions for making chlorion and its dissolving stay in about 10~
In 20% strong brine, this part strong brine is less due to water, and the grey field for industrial and mining enterprises carries out sprinkling processing, and it is thrown
Money and operating cost can be well below the only progress pretreated evaporation treatment process of dosing.
Chinese patent application 201010196948.0 discloses the method and dress of a kind of electric flocculation recovering and processing desulfurized wastewater
Put, desulfurization wastewater enters electric flocculation reactor through collecting, and then carries out separation of solid and liquid, the clarification and effluent after separation is back to electricity
Factory rushes ash-slag disposal system or directly discharge, and body refuse is transported to sludge treating system and is dehydrated, and the water outlet of sludge treating system is returned
It flow to water inlet system.The pollutant in waste water can be effectively removed, the handling rate of heavy metal is up to 95%~99%, to chlorine
Handling rate is up to clearances such as more than 80%, COD, ammonia nitrogens up to more than 90%.
Chinese patent application 201510510203.X is related to a kind of while removing the SS of desulfurization wastewater middle and high concentration, fluorination
Thing, sulfate, arsenate and COD processing unit and processing method.The characteristics of processing unit is：Sedimentation basin overfall passes through
Pipeline and a delivery pump connection, primary-clarifiers agitating device are arranged on primary-clarifiers, and No. two delivery pumps pass through pipeline
With the connection of the 3rd reaction chamber.The step of processing method is：Desulfurization wastewater, which enters sedimentation basin, to be carried out after primary precipitation, and water outlet is successively
Chemistry-coagulating sedimentation reaction is carried out into the first reaction chamber, the second reaction chamber, primary-clarifiers is entered back into and carries out separation of solid and liquid；
Supernatant introduces the 3rd reaction chamber, and reacted mixed liquor sequentially enters flocculation tanks, Secondary clarifier, flocculated respectively again
Reaction and clarification concentration；Supernatant introduces filter and filtered, and water outlet regulation pH is 6~9.
Chinese patent application 200920146366.4 is disclosed in a kind of field of Environment Protection water treatment system, it is adaptable to boiler smoke
The Waste Water Treatment device used in desulfurization, denitration wastewater processing system.In the system and device, there is provided waste water
Regulating box, integrated box, fluorine removal reaction chamber, clarifier, sludge concentrator, sludge storage tank, plate and frame filter press, bucket and it is a variety of from
Dynamic chemicals dosing plant, system automation degree is high, employs PLC closed loop measurement and controls and PID regulations.
Although three kinds of technologies such as overcritical electric coagulation, the mixed inclined plate sedimentation of change and Defluorination of Formation Mater By Adsorption On Activated Alumina absorption respectively have accordingly
The scope of application, all sporadically appears in open source literature, but in terms of desulfurization wastewater fluorine removal, this three kinds of technologies do not disclose usability methods.
The content of the invention
Defluorination method is integrated it is an object of the invention to provide Desulphurization for Coal-fired Power Plant waste water, prior art defect is overcome, protected
On the premise of card water outlet fluorine ion is up to standard, added amount of chemical is reduced, the fluorine-containing dirt obtained in cost, wastewater treatment process is reduced
Mud settleability is good, and dewatering is good and sludge quantity greatly reduces, and realizes fluorine-containing sludge minimizing.
The purpose of the present invention will be realized by following technical measures：Enter successively after the repeated pond of desulfurization wastewater and jogging groove
Enter mixed groove and stillpot slowly, wherein add bleaching water in relaying pond and jogging groove, in slow mixed groove addition PAC with
Polymer, precipitating sludge is excluded into extruder processing by stillpot；Stillpot shunting treatment fluid introduces intermediate pool, Ran Houyin
Enter overcritical electric coagulation apparatus, successively NaOH is mixed soon plus polymer is mixed slowly by adding subsequently into mixed inclination plate settling facility is changed
PH9~10 are adjusted, settled sludge squeezes into extruder, and the mixed inclination plate settling facility shunting treatment fluid of change introduces work after adding HCL tune pH6~9
Property aluminum oxide equipment release outer behind pond arrange being introduced after Defluorination of Formation Mater By Adsorption On Activated Alumina agent filter is heavy.
Especially, production method comprises the following steps：
1) just precipitate：In desulfurization wastewater add bleaching water to NH3-N concentration be below 20mg/L, then add PAC and
Polymer, makes to precipitate at the beginning of desulfurization wastewater, removes suspended solid and part fluorine ion in desulfurization wastewater, and this walks out of water pH and is about
6~8；
2) overcritical electric coagulation：Just supernatants after precipitation enters overcritical electric coagulation apparatus to desulfurization wastewater, based on electrochemistry
Treatment technology principle, electrolysis produces the hydroxide of aluminium, and sediment is produced with fluorine ion reaction, is given up so as to remove desulfurization
Fluorine ion in water, water outlet pH is 5~7；
3) mixed inclined plate sedimentation is changed：A certain amount of NaOH is added into the desulfurization wastewater after overcritical electric coagulation technology processing
Then solution, regulation pH adds high polymer material and flocculate is settled 9~10.
4) Defluorination of Formation Mater By Adsorption On Activated Alumina agent is adsorbed：Desulfurization wastewater is after changing mixed inclined plate sedimentation, and supernatant enters activated alumina and set
Standby absorption, can be down to below 5ppm, it is ensured that desulfurization wastewater qualified discharge by fluorinion in waste water.
Especially, overcritical electric coagulation apparatus are used as reaction electrode, positive pole and negative pole Automatic pole changing, electricity using aluminum pole
Stream uses overload protection mechanism, and current limit is 100A；The overcritical electric coagulation of overcritical electric coagulation apparatus includes three continuously
Stage：1) anode produces the hydroxide for electronically forming tiny flocculation agent, i.e. iron or aluminium；2) particle, the colloid suspended in water
Pollutant loss of stability in the presence of flocculant, destroys pollutant surface-stable degree；3) contaminant particle and tiny flocculation agent
Between mutually collide, absorption, in and/or cohesion form compared with big flocculating body.
Especially, Defluorination of Formation Mater By Adsorption On Activated Alumina agent specific surface area 330m2/ g, adsorption capacity is 1 ‰~3 ‰, 1~3mm of granularity.
Especially, the high-frequency impulse course of work of overcritical electric coagulation apparatus includes：By high frequency pulse power supply high-frequency weight
Multiple " power supply-power-off is powered " process, ion concentration can be reduced rapidly during power supply, during power-off ion concentration can supplement rapidly with it is extensive
Multiple, during this pulse electrolysis, conduction time, which is less than, is electrolysed total reaction time, and dissolving metal amount is less than DC electrolysis
Meltage, thus the polarization of reduction concentration difference and power consumption, moreover, the ripple sent every one identical time, can dash forward in a short time
Become, the physical quantity of its initial value is then rapidly returned to again；At the same time, direct impulse is followed by reverse impulse, is kept for two polar periods
Commutation change, prevents electrode passivation.
Advantages of the present invention and effect：By overcritical electric coagulation, change mixed inclined plate sedimentation and Defluorination of Formation Mater By Adsorption On Activated Alumina absorption three
The technology of kind is mutually coordinated to support integration to be integrated, and overcomes prior art defect, makes full use of the advantage of every kind of technology, is ensureing
On the premise of water outlet fluorine ion is up to standard, added amount of chemical is reduced, the fluorine-containing sludge obtained in cost, wastewater treatment process is reduced
Settleability is good, and dewatering is good and sludge quantity greatly reduces, and realizes fluorine-containing sludge minimizing.Waste water is carried out using electrolytic cell
On electric flocculation basis, high-frequency impulse technology is merged, makes equipment during waste water is handled while having electrocoagulation, electricity
The multiple degrading such as air supporting and electrochemical redox is acted on, and substantially increases the clearance of pollutant, while reducing concentration pole
Change and prevention electrode passivation problem, significantly extend electrode life and improve electric current conduction efficiency.Processing procedure simple and effective, behaviour
Make automaticity high.System run all right is reliable, and energy consumption is low, and operating cost is low, and substantially reduces processing time, environmental protection
Performance is good, it is ensured that water outlet reaches discharge standard, and can save a large amount of medicaments.
Brief description of the drawings
Fig. 1 is desulfurization wastewater defluorination method schematic diagram in the prior art.
Fig. 2 is desulfurization wastewater defluorination method schematic diagram in the embodiment of the present invention 1.
Fig. 3 is the high-frequency impulse operation principle schematic diagram of overcritical electric coagulation apparatus in the present invention.
Embodiment
The principle of the invention is, for the characteristics of fluorine-containing excursion is wider in Desulphurization for Coal-fired Power Plant waste water, firstly, since
Desulfurization wastewater is to wash buck from coal-burning power plant, itself contains more lime-ash and sludge components, if without preliminary heavy
Form sediment, directly carry out overcritical electric coagulating treatment, then have a strong impact on electric coagulation effect；Secondly, fluorinion concentration ＞ in desulfurization wastewater
, it is necessary to which adding excessive liquid caustic soda progressization mixes inclined plate sedimentation, so that it is larger to produce sludge quantity during 120mg/L.And desulfurization wastewater
In contain be more than the substantial amounts of sulfate ions of 20000mg/L and a large amount of metal magnesium ions, proved by many experiments result, if
Liquid caustic soda sedimentation is directly added into, then easily produces in sulfuric acid magnesium precipitate, increase sludge quantity, and sludge and contains a large amount of sodium sulphate, hydrogen-oxygen
Change magnesium, then it is difficult dehydration to cause sludge, but use overcritical electric coagulation apparatus, pass through what is discharged on quick exciting electrode plate
Ion, electrolysis forms the hydroxide that " tiny flocculation agent " is aluminium, precipitation is quickly formed with fluorine ion in desulfurization wastewater, during reaction
Between it is short, it is to avoid the formation of sulfuric acid magnesium precipitate, sludge quantity is smaller, and the condition such as comprehensive power consumption and aluminium sheet consumption is weighed, overcritical electricity
Coagulation fluorine removal can only make fluorine ion be down to tens of ppm；In addition, when fluorinion concentration is down to tens of ppm, adding appropriate liquid caustic soda
Progressization mixes inclined plate sedimentation, and fluorine ion can be down within 10mg/L, and many experiments result is proved, adds liquid caustic soda by fluorine ion
When concentration is down to 1~2mg/L by 10mg/L or so, a large amount of liquid caustic soda need to be added, sludge quantity are produced excessive.And desulfurization wastewater is placed
Time, fluorine ion was easily discharged after long afterwards, so caused the desulfurization wastewater discharge of Duo Jia steam power plants can not be up to standard, influence is just
Often production, activated alumina absorption is added in end, because activated alumina absorption is only applicable to fluorinion concentration and is less than
10mg/L water fluoridation, therefore the performance of activated alumina can be made full use of, it is ensured that water outlet fluorine ion is up to standard.Last swash plate sinks
Drop plus alkali sludge and leading portion add after PAC stillpot to come out sludge to be mixed into extruder processing, can overcome plus alkali sludge takes off
The problem of shipwreck.
In the present invention, as shown in Figure 2, production method comprises the following steps：
1) just precipitate：It is below 20mg/L that bleaching water to NH3-N concentration is added in desulfurization wastewater, then adds weight percent
Than PAC and polymer, make to precipitate at the beginning of desulfurization wastewater, remove the suspended solid and part fluorine ion in desulfurization wastewater, this is walked out of
Water pH is about 6~8.
2) overcritical electric coagulation technology：Just supernatants after precipitation enters overcritical electric coagulation apparatus to desulfurization wastewater, based on electricity
Chemical treatment method principle, electrolysis produces the hydroxide of aluminium, sediment is produced with fluorine ion reaction, so as to remove de-
Fluorine ion in sulphur waste water, it is about 5~7 that this, which walks out of water pH,.
3) mixed inclined plate sedimentation is changed：A certain amount of NaOH is added into the desulfurization wastewater after overcritical electric coagulation technology processing
Solution, pH is 9~10 for regulation, then adds a small amount of macromolecule so that flocculate is settled.
4) Defluorination of Formation Mater By Adsorption On Activated Alumina agent is adsorbed：Desulfurization wastewater is after changing mixed inclined plate sedimentation, and supernatant enters activated alumina suction
It is attached, fluorinion in waste water can be down to below 5ppm, it is ensured that desulfurization wastewater qualified discharge.
In abovementioned steps (2), overcritical electric coagulation apparatus are that one kind processing based on electrochemical treatments technical principle is highly concentrated
Degree, high chroma, difficult degradation, poisonous organic pollution and set containing heavy metal, the new of fluorine-containing, the various industrial wastewaters containing cyanogen etc.
It is standby.The overcritical electric coagulation apparatus have the characteristics of high voltage, high current, height release energy；With on quick exciting electrode plate
Plasma diffusing W,Mo, and burst size it is big the characteristics of；Both positive and negative polarity switching is carried out with quick, so as to reduce electrode passivation, concentration is reduced
The characteristics of polarization and power consumption.The overcritical electric coagulation apparatus are using aluminum pole as reaction electrode, and positive pole is automatic with negative pole
Change poles, can extend electrode usage cycles.The overcritical electric coagulation apparatus electric current uses overload protection mechanism, electric current during work
Depending on water quality information, current limit is 100A, and current overload, protection mechanism starts；Meanwhile, the overcritical electric coagulation
Including three continuous stages：
1) anodes produce the hydroxide for electronically forming tiny flocculation agent, i.e. iron or aluminium, contribute to the electrolysis of anode；
2) particle, the colloid pollution thing loss of stability in the presence of flocculant suspended in water, destruction pollutant surface
Stability；
3) mutually collided between contaminant particles and tiny flocculation agent, absorption, in and/or cohesion form compared with big flocculating body；
In abovementioned steps (3), NaOH solution is added, fluorinion concentration can be down to very low dense by regulation pH 9~10
Degree, wherein optimal pH are 9.5~10.
In abovementioned steps (4), Defluorination of Formation Mater By Adsorption On Activated Alumina agent specific surface area 330m2/ g, adsorption capacity is 1 ‰~3 ‰, granularity
1~3mm.
In foregoing, as shown in Figure 3, the high-frequency impulse operation principle of overcritical electric coagulation apparatus includes：By high-frequency impulse
Power supply high-frequency repeats " power supply-power-off is powered " process, and ion concentration can be reduced rapidly during power supply, ion concentration meeting during power-off
Rapid supplement and recovery, during this pulse electrolysis, conduction time, which is less than, is electrolysed total reaction time, dissolving metal amount
Less than DC electrolysis meltage, thus concentration difference polarization and power consumption are reduced, moreover, the ripple sent every one identical time, meeting
It is mutated in a short time, the physical quantity of its initial value is then rapidly returned to again；At the same time, direct impulse is followed by reverse impulse,
The change of the two poles of the earth periodic reverse is kept, electrode passivation is prevented.
The invention will be further described with reference to the accompanying drawings and examples.
Embodiment 1：As shown in Figure 2, desulfurization wastewater water is 200CMD, and pH is 7.63, wherein, fluorinion concentration is
183mg/L, ammonia-nitrogen content is 30.5mg/L, and sulfate ion concentration is 32500mg/L, and desulfurization wastewater respectively enters relaying pond
And dashpot, add bleaching water and ammonia nitrogen is down to below 20mg/L, subsequently into slow mixed groove, 0.2CMD is added in slow mixed groove
The 10%PAC and polymer of 0.2CMD 2 ‰, stirring is sufficiently mixed it, and treatment fluid squeezes into stillpot, produces after settlement
Sludge is delivered to extruder press filtration, and water outlet enters intermediate pool, and now water outlet pH is about 6.78, and fluorinion concentration is 128mg/L,
Ammonia-nitrogen content is 16.9mg/L, and sulfate ion concentration is 32000mg/L；Fluoride waste in intermediate pool enters overcritical electricity
Coagulation apparatus, 5~10A of operation electric current, temperature 50 C or so, 2~4min of time, water outlet pH is 5.45, fluorine ion after processing
Concentration is 46.9mg/L, and sulfate ion concentration is 32000mg/L；Entered by overcritical electric coagulation apparatus water outlet through going out water pump
Change mixed inclination plate settling facility, it is divided into mixes, mixes three processes of inclined plate sedimentation slowly soon, in fast mixed stage, addition about 2.4CMD
30%NaOH, quick stirring reaction, in the slow mixed stage, adds the polymer of 0.4CMD 2 ‰, produces bulky grain glue plumage and is beneficial to sink
Drop, the sludge produced after inclined plate sedimentation is delivered to filter press press filtration, and water outlet is adsorbed into activated alumina, now water outlet pH
For 9.75, fluorinion concentration is 10.52mg/L, and sulfate ion concentration is 32000mg/L；Add 0.4CMD 1%HCl solution
PH is adjusted to neutrality, is adsorbed subsequently into activated alumina groove, water outlet fluorinion concentration is 4.2mg/L, sulphur after absorption 30min
Acid ion concentration is 28500mg/L, up to standard can import and release pond discharge；After being handled through this process, about 5.9 tons are produced daily
The fluorine-containing sludge of moisture content 75%, about 15.8 yuan/m of processing cost3。
Compareed with prior art, i.e., desulfurization wastewater water is 200CMD, and pH is 7.63, and fluorinion concentration is 183mg/L,
Ammonia-nitrogen content is 30.5mg/L, and sulfate ion concentration is 32500mg/L desulfurization wastewater, into relaying pond and dashpot, is added
Plus ammonia nitrogen is down to below 20mg/L by bleaching water, subsequently into slow mixed groove, 4.5CMD alkali manganese solution is added in slow mixed groove,
0.01CMD recaptures agent, and the polymer of 2CMD 10%PAC and 1CMD 2 ‰, stirring is sufficiently mixed it, then squeezes into stillpot,
The sludge produced after settlement is delivered to extruder press filtration, and water outlet entrance releases pond and released, and water outlet pH is about 9.59, fluorine ion
Concentration is 5.71mg/L, and ammonia-nitrogen content is 16.9mg/L, and sulfate ion concentration is 27500mg/L；It is treated through this waste water original
After journey processing, the fluorine-containing sludge of about 12.7 tons of moisture content 75%, about 23.2 yuan/m of processing cost are produced daily3。
Contrasted by both the above case study on implementation, it is clear that the present invention makes full use of the advantage of every kind of technology, ensureing water outlet fluorine
On the premise of ion is up to standard, added amount of chemical is reduced, cost is reduced, sludge quantity is reduced, realizes fluorine-containing sludge minimizing.
Embodiment 2：In embodiment 1, overcritical electric coagulation, direct liquid feeding alkali process are omitted：Desulfurization wastewater pH is 7.63,
Fluorinion concentration is 183mg/L, and ammonia-nitrogen content is 30.5mg/L, and sulfate ion concentration is 32500mg/L；It is useless to the desulfurization
Bleaching water is added in water ammonia nitrogen is down to below 20mg/L, then add the polymer of 1mL/L 10%PAC and 2mL/L 2 ‰,
Stirring is sufficiently mixed it, and supernatant pH is about 6.78 after settlement, and fluorinion concentration is 128mg/L, and ammonia-nitrogen content is
16.9mg/L, sulfate ion concentration is 32000mg/L；About 0.5mL/L 30%NaOH are added after filter sludge, in supernatant,
Quick stirring reaction, then adds the polymer of 2mL/L 2 ‰, and slowly stirring produces the sedimentation of bulky grain glue plumage, and supernatant pH is about
For 8.98, fluorinion concentration is 127mg/L, and sulfate ion concentration is 26000mg/L, and thus data are understood, work as desulfurization wastewater
When middle fluorinion concentration is higher, add that liquid caustic soda solution settles first is sulfate ion rather than fluorine ion；Added in supernatant
Then about 47.2mL/L 30%NaOH, quick stirring reaction adds the polymer of 10mL/L 2 ‰, and slowly stirring produces big
The plumage sedimentation of grain glue, supernatant pH is about 10.1, and fluorinion concentration is 1.39mg/L, and sulfate ion concentration is 25700mg/L,
Calculated according to water 200CMD, the fluorine-containing sludge of about 16.4 tons of moisture content 75% is produced daily, thus data are understood, are added
Fluorinion concentration can be down to very low by amount liquid caustic soda solution, but add liquid caustic soda solution to after certain pH value, add liquid caustic soda molten
Liquid, settles more for magnesium ion, generates magnesium hydrate precipitate, causes sludge quantity excessive and sludge is difficult dehydration, this pH scope
It is less than 9.8 or so for pH.
The present invention merges high-frequency impulse technology, made on the basis of traditional progress Wastewater by Electric flocculating principles using electrolytic cell
Equipment has the effect of the multiple degradings such as electrocoagulation, electric floating and electrochemical redox simultaneously during waste water is handled,
The clearance of pollutant is substantially increased, while reducing concentration polarization and prevention electrode passivation problem, significantly extends electrode life
And improve electric current conduction efficiency.
Technological means disclosed in the present invention program is not limited only to the technological means disclosed in above-mentioned embodiment, in addition to
Constituted technical scheme is combined by above technical characteristic.It should be pointed out that for those skilled in the art
For under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications are also considered as
Protection scope of the present invention.
Claims (5)
1. Desulphurization for Coal-fired Power Plant waste water integrate sequentially entered behind defluorination method, the repeated pond of desulfurization wastewater and jogging groove mixed groove slowly and
Stillpot, wherein adding bleaching water in relaying pond and jogging groove, adds PAC and Polymer in slow mixed groove, is arranged by stillpot
Except precipitating sludge is handled into extruder；Characterized in that, stillpot shunting treatment fluid introduces intermediate pool, then introduce overcritical
Electric coagulation apparatus, subsequently into change mixed inclination plate settling facility successively by plus NaOH mix soon plus polymer mix slowly adjust pH9~
10, settled sludge squeezes into extruder, changes mixed inclination plate settling facility shunting treatment fluid and adds HCL to introduce activated alumina after adjusting pH6~9
Equipment is outer after introducing after being sunk by Defluorination of Formation Mater By Adsorption On Activated Alumina agent filter releases pond to arrange.
2. Desulphurization for Coal-fired Power Plant waste water as claimed in claim 1 integrates defluorination method, it is characterised in that production method is included such as
Lower step：
1) just precipitate：In desulfurization wastewater add bleaching water to NH3-N concentration be below 20mg/L, then add PAC and
Polymer, makes to precipitate at the beginning of desulfurization wastewater, removes suspended solid and part fluorine ion in desulfurization wastewater, it is about 6 that this, which walks out of water pH,
~8；
2) overcritical electric coagulation：Just supernatants after precipitation enters overcritical electric coagulation apparatus to desulfurization wastewater, based on electrochemical treatments
Technical principle, electrolysis produces the hydroxide of aluminium, sediment is produced with fluorine ion reaction, so as to remove in desulfurization wastewater
Fluorine ion, water outlet pH is 5~7；
3) mixed inclined plate sedimentation is changed：It is molten that a certain amount of NaOH is added into the desulfurization wastewater after overcritical electric coagulation technology processing
Then liquid, regulation pH adds high polymer coagulant and flocculate is settled 9~10.
4) Defluorination of Formation Mater By Adsorption On Activated Alumina agent is adsorbed：Desulfurization wastewater is after changing mixed inclined plate sedimentation, and supernatant enters the suction of activated alumina equipment
It is attached, fluorinion in waste water can be down to below 5ppm, it is ensured that desulfurization wastewater qualified discharge.
3. Desulphurization for Coal-fired Power Plant waste water as claimed in claim 1 integrates defluorination method, it is characterised in that overcritical electric coagulation is set
Standby to use aluminum pole as reaction electrode, positive pole and negative pole Automatic pole changing, electric current uses overload protection mechanism, and current limit is
100A；The overcritical electric coagulation of overcritical electric coagulation apparatus includes three continuous stages：1) anode produces and electronically forms micro- wadding
The hydroxide of solidifying agent, i.e. iron or aluminium；2) particle, the colloid pollution thing suspended in water loses stabilization in the presence of flocculant
Property, destroy pollutant surface-stable degree；3) mutually collided between contaminant particle and tiny flocculation agent, absorption, in and/or cohesion knot
Into compared with big flocculating body.
4. Desulphurization for Coal-fired Power Plant waste water as claimed in claim 1 integrates defluorination method, it is characterised in that Defluorination of Formation Mater By Adsorption On Activated Alumina
Agent specific surface area 330m2/ g, adsorption capacity is 1 ‰~3 ‰, 1~3mm of granularity.
5. Desulphurization for Coal-fired Power Plant waste water as claimed in claim 1 integrates defluorination method, it is characterised in that overcritical electric coagulation is set
The standby high-frequency impulse course of work includes：By high frequency pulse power supply high-frequency repeat " power supply-power-off is powered " process, during power supply from
Sub- concentration can be reduced rapidly, and ion concentration can be supplemented and recovered rapidly during power-off, during this pulse electrolysis, conduction time
Less than total reaction time is electrolysed, dissolving metal amount is less than DC electrolysis meltage, thus the polarization of reduction concentration difference and power consumption, and
And, the ripple sent every one identical time can be mutated in a short time, and the physical quantity of its initial value is then rapidly returned to again；
At the same time, direct impulse is followed by reverse impulse, keeps the change of the two poles of the earth periodic reverse, prevents electrode passivation.
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| CN109626521A (en) * | 2019-01-25 | 2019-04-16 | 新乡市蓝海环境科技有限公司 | High-frequency impulse electrochemistry handles fluoride waste method and device thereof |
| CN110078249A (en) * | 2018-01-25 | 2019-08-02 | 宝山钢铁股份有限公司 | Remove the deep treatment method and system of COD and total iron in power plant desulfurization wastewater |
| CN114835282A (en) * | 2022-03-25 | 2022-08-02 | 石家庄新奥环保科技有限公司 | Supercritical water oxidation treatment wastewater control system |
| CN115043519A (en) * | 2022-05-26 | 2022-09-13 | 太原水质监测站有限公司 | Reaction tank for simultaneously removing arsenic and fluorine in underground water |
| CN115415277A (en) * | 2021-05-12 | 2022-12-02 | 上海交通大学 | Harmless treatment method for secondary aluminum ash |
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