CN110127918B - Zero-discharge treatment method and device for acidic flue gas washing wastewater - Google Patents
Zero-discharge treatment method and device for acidic flue gas washing wastewater Download PDFInfo
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- CN110127918B CN110127918B CN201810106012.0A CN201810106012A CN110127918B CN 110127918 B CN110127918 B CN 110127918B CN 201810106012 A CN201810106012 A CN 201810106012A CN 110127918 B CN110127918 B CN 110127918B
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- flue gas
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- 239000002351 wastewater Substances 0.000 title claims abstract description 233
- 238000000034 method Methods 0.000 title claims abstract description 188
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 156
- 239000003546 flue gas Substances 0.000 title claims abstract description 156
- 238000005406 washing Methods 0.000 title claims abstract description 133
- 230000002378 acidificating effect Effects 0.000 title claims abstract description 113
- 208000028659 discharge Diseases 0.000 title claims abstract description 29
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 184
- 239000003513 alkali Substances 0.000 claims abstract description 93
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 90
- 238000005189 flocculation Methods 0.000 claims abstract description 76
- 230000016615 flocculation Effects 0.000 claims abstract description 76
- 238000001914 filtration Methods 0.000 claims abstract description 72
- 238000001556 precipitation Methods 0.000 claims abstract description 68
- 239000000428 dust Substances 0.000 claims abstract description 62
- 230000008569 process Effects 0.000 claims abstract description 56
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 34
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 34
- 238000001035 drying Methods 0.000 claims abstract description 29
- 238000002425 crystallisation Methods 0.000 claims abstract description 25
- 230000008025 crystallization Effects 0.000 claims abstract description 25
- 239000000126 substance Substances 0.000 claims abstract description 24
- 238000004064 recycling Methods 0.000 claims abstract description 21
- 239000006227 byproduct Substances 0.000 claims abstract description 18
- 239000000460 chlorine Substances 0.000 claims abstract description 18
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 17
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 17
- 239000011737 fluorine Substances 0.000 claims abstract description 17
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims description 114
- 150000003839 salts Chemical class 0.000 claims description 110
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 81
- 229910052751 metal Inorganic materials 0.000 claims description 74
- 239000002184 metal Substances 0.000 claims description 74
- 239000002253 acid Substances 0.000 claims description 61
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 46
- 239000007789 gas Substances 0.000 claims description 44
- 239000003344 environmental pollutant Substances 0.000 claims description 43
- 238000001179 sorption measurement Methods 0.000 claims description 40
- 230000003647 oxidation Effects 0.000 claims description 39
- 238000007254 oxidation reaction Methods 0.000 claims description 39
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 32
- 239000010802 sludge Substances 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 28
- 239000002244 precipitate Substances 0.000 claims description 28
- 238000011084 recovery Methods 0.000 claims description 27
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 21
- 239000003463 adsorbent Substances 0.000 claims description 20
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 18
- 238000005200 wet scrubbing Methods 0.000 claims description 16
- 239000003929 acidic solution Substances 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 12
- 150000002739 metals Chemical class 0.000 claims description 11
- 231100000719 pollutant Toxicity 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 10
- 239000004744 fabric Substances 0.000 claims description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 238000000889 atomisation Methods 0.000 claims description 8
- 239000002585 base Substances 0.000 claims description 8
- 239000002957 persistent organic pollutant Substances 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052793 cadmium Inorganic materials 0.000 claims description 7
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 239000011133 lead Substances 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 239000011575 calcium Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 230000005484 gravity Effects 0.000 claims description 6
- 239000012528 membrane Substances 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 5
- 239000000919 ceramic Substances 0.000 claims description 5
- 238000006056 electrooxidation reaction Methods 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- 229910000831 Steel Inorganic materials 0.000 claims description 4
- 239000004566 building material Substances 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000011736 potassium bicarbonate Substances 0.000 claims description 4
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 4
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 4
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 239000010959 steel Substances 0.000 claims description 4
- 239000012855 volatile organic compound Substances 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 239000002608 ionic liquid Substances 0.000 claims description 3
- 239000012621 metal-organic framework Substances 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 235000011181 potassium carbonates Nutrition 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 239000003814 drug Substances 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 21
- 238000009833 condensation Methods 0.000 abstract description 17
- 230000005494 condensation Effects 0.000 abstract description 17
- 230000009467 reduction Effects 0.000 abstract description 9
- 239000002920 hazardous waste Substances 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 description 14
- 239000011593 sulfur Substances 0.000 description 13
- 229910052717 sulfur Inorganic materials 0.000 description 13
- 238000003795 desorption Methods 0.000 description 11
- 150000002500 ions Chemical class 0.000 description 10
- 230000009471 action Effects 0.000 description 9
- -1 ammonium ions Chemical class 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 150000001768 cations Chemical class 0.000 description 7
- 239000002918 waste heat Substances 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000004065 wastewater treatment Methods 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 230000003311 flocculating effect Effects 0.000 description 4
- OMRRUNXAWXNVFW-UHFFFAOYSA-N fluoridochlorine Chemical class ClF OMRRUNXAWXNVFW-UHFFFAOYSA-N 0.000 description 4
- 238000005469 granulation Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- 238000009388 chemical precipitation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000003916 acid precipitation Methods 0.000 description 2
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
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- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 210000002966 serum Anatomy 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000192710 Microcystis aeruginosa Species 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000003921 particle size analysis Methods 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/18—Absorbing units; Liquid distributors therefor
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
-
- 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
- C02F1/02—Treatment of water, waste water, or sewage by heating
-
- 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
- C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- 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
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
-
- 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
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Treating Waste Gases (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention provides a zero discharge treatment method of acidic flue gas washing wastewater, which removes suspended matters in the wastewater through acidic filtration; removing metal ions by flocculation precipitation; then, substances such as fluorine, chlorine and the like are recovered through drying, and organic substances are removed; or recovering ammonia-containing by-products by a high-alkali ammonia removal process, and recovering substances such as fluorine, chlorine and the like by condensation crystallization. The method can effectively treat the acidic washing wastewater, realizes the reduction of heavy metal hazardous waste, clean treatment and recycling of ammonia nitrogen, and avoids the blockage of equipment by elemental sulfur, zero discharge of wastewater, low dust viscosity and no bag pasting phenomenon; the resources are recovered and reused, and the environment is protected.
Description
Technical Field
The invention relates to a wastewater treatment method, in particular to a treatment method and a device for acidic flue gas washing wastewater. Belonging to the field of resource environment protection.
Background
Sulfur dioxide is one of main atmospheric pollutants in China, and the annual emission amount is nearly 2000 million tons, so that serious sulfur resource waste and atmospheric environmental pollution such as acid rain, haze and the like are caused. With the strictness of national environmental laws and regulations and standards, the realization of the emission reduction and the recovery of sulfur dioxide becomes a major issue to be urgently broken through in the environmental protection field. Sulfuric acid is used as an important chemical raw material and widely applied to industrial production, while the sulfur resource in China is relatively short, and the supply of sulfuric acid is short for a long time. After the sulfur resource in the sulfur dioxide is changed into the sulfuric acid, the condition of shortage of the sulfur resource in China can be effectively relieved, the pollution of the sulfur dioxide to the environment can be reduced, and meanwhile, certain benefits are brought to enterprises.
At present, the process for converting sulfur dioxide into sulfuric acid mainly comprises the steps of absorbing low-concentration sulfur dioxide by using a solid adsorbent or liquid, and then enriching the sulfur dioxide into high-concentration sulfur dioxide by resolution for preparing sulfuric acid. In order to ensure the quality of sulfuric acid and the stability of an acid making system, a washing method is often adopted to wash and remove impurities from the analytic gas, so that a large amount of acidic flue gas washing wastewater is generated.
Since the stripping gas often contains a large amount of sulfur dioxide, it is dissolved into water during the washing process, so that the washing wastewater is generally acidic. The washing wastewater components are easily affected by sulfur dioxide flue gas, an adsorbent and a desorption process, so that the washing wastewater components are various, and the impurities in the desorption gas are complex and high in concentration, so that the washing wastewater components are particularly complex.
Through earlier stage research, the acid-making wastewater is determined to be mainly complex wastewater containing elemental sulfur, suspended matters, metals, ammonia nitrogen, fluorine and chlorine and organic pollutants. However, at present, the wastewater is not effectively treated, and a reference technology is not available at home and abroad.
Ammonia nitrogen is one of main pollutants in a water body, and the main harm of the ammonia nitrogen to the environment is to cause eutrophication phenomena such as red tide, water bloom and the like, thereby seriously threatening ecological safety. Aiming at the common methods for removing ammonia nitrogen in wastewater, such as a chemical precipitation method, a stripping method, a chemical oxidation method, a biological method, a membrane separation method, an ion exchange method and the like. The discharge of large amounts of wastewater containing metal ions such as iron, copper, lead, zinc, cadmium, cobalt, nickel, etc. also poses a great hazard to the environment and human health. The common metal wastewater treatment methods include a chemical precipitation method, an extraction method, a flotation method, an adsorption method, an ion exchange method, an electrochemical deposition method and the like. While chemical precipitation is the most mature and widely used method. However, in the actual industry, the wastewater contains only ammonia nitrogen or metal ions, and both of them are often coexistent. Such as waste water from hydrometallurgy, electroplating, PCB (printed circuit board), rare earth production, landfill, etc. Although a great deal of research has been carried out on the treatment of the composite wastewater at present, no good treatment effect can be obtained. For example, patent CN 103964612B reports a method for treating middle and low concentration ammonia nitrogen wastewater with high COD, high salt content and high heavy metal content, which comprises the specific steps of adjusting the pH of the wastewater to 9-11, so as to convert ammonium ions (NH4+) in the wastewater into volatile NH 3; removing metal ions after flocculation precipitation and filtration; thereby achieving the purpose of removing ammonia nitrogen and metal ions. For another example, patent CN 102942280 a reports a decomplexation method of heavy metal ammonia complex in high concentration ammonia nitrogen wastewater, which specifically comprises adjusting the pH of the wastewater to 9-11, so that ammonium ions are converted into ammonia molecules and redundant hydroxyl ions exist; the temperature distribution of the stripping tower is controlled by controlling the steam flow and the steam pressure input into the stripping tower, so that the liquid is kept for a certain retention time in a certain temperature area in the stripping tower, the heavy metal ammonia complex is decomposed, and heavy metal ions are combined with redundant hydroxyl ions in the wastewater to generate precipitate.
As mentioned above, in the prior art, the treatment of high ammonia nitrogen wastewater containing metal ions is carried out by adjusting the solution to high alkalinity to precipitate all the metal ions, and then treating ammonia nitrogen. However, under high alkali conditions, the metal cations are easy to form stable complexes with ammonia nitrogen, so that the removal rate of the metal cations and the ammonia nitrogen is reduced. In addition, the solution is in a high-alkali state, and although metal cations can be precipitated, ammonia nitrogen can be converted into free ammonia in high alkalinity, so that the ammonia can be separated out from a liquid phase, and a large amount of ammonia can escape. However, adjusting the solution to a lower alkalinity is not conducive to complete precipitation of the metal cations. In order to effectively solve the above-mentioned contradiction and realize the effective removal of metal cations and ammonia nitrogen, a novel cleaning treatment technology is urgently needed to be developed.
Because the traditional wastewater treatment process has the problems of long flow, more equipment, high operating cost and the like, the flue gas has the waste heat, and the characteristic of drying the wastewater is realized, the desulfurized wastewater is atomized and dried to form dry ash, and then is captured and removed by dust removal equipment. Has simple process, small occupied area and capability of removing soluble salt, such as Cl, which cannot be treated by the traditional chemical process-And the like, realizes zero discharge of wastewater, and is more and more concerned. However, the technology of drying the acidic washing wastewater by using the residual heat of the flue gas has not been reported, and the application of the current technology to the drying of the acidic washing wastewater has various disadvantages. For example, patent CN 106145230A reports a system for treating desulfurized wastewater by using waste heat of flue gas, which is specifically operated by using the waste heat of the wastewaterSpraying the mixture into a spray tower, evaporating the waste water by using the waste heat of the flue gas, feeding the waste water after most of water is evaporated into a concentration tank, and finally discharging the waste water after pressure filtration. The method is only used for concentrating the wastewater, the complete drying of the wastewater is not realized, and the wastewater is directly evaporated and dried without other treatment. In practical application, the concentrated solution is difficult to treat, and a large amount of metal-containing sludge is generated. As patent CN 106630259 a reports a system for zero discharge of waste water at the end of a power plant, specifically, firstly, adjusting waste water to be more than 10 by using alkali liquor, then, after solid-liquid separation, returning waste water with low conductivity for desulfurization, adding acid into waste water with high conductivity to adjust pH back to 6-7, and then, sequentially passing through a filtering system, an atomizing system and a drying system to realize drying and zero discharge of waste water. The method is a conventional wastewater drying treatment process, and obviously cannot be directly used for treating acid washing wastewater. If the method firstly directly adjusts the wastewater to high alkali, because the acidic washing wastewater often contains elemental sulfur, the elemental sulfur is dissolved and changed into sodium thiosulfate if not removed in advance, and finally the elemental sulfur is decomposed into sulfur during drying, so that equipment is blocked. In addition, in the method, ammonia nitrogen in the wastewater cannot be volatilized when the wastewater is adjusted to be neutral during drying, ammonium sulfate or ammonium bisulfate is easily formed during drying, the viscosity of dry ash is increased, and bag pasting of the dust remover is caused. In order to effectively solve the problems and realize the clean treatment and zero discharge of the acidic washing wastewater, a novel clean treatment technology aiming at the characteristics of the acidic washing wastewater is urgently needed to be developed.
Disclosure of Invention
Aiming at the characteristic that the acid washing wastewater in the prior art is complex wastewater containing elemental sulfur, suspended matters, metals, ammonia nitrogen, fluorine and chlorine and organic pollutants; the invention provides a treatment method for zero discharge of acidic flue gas washing wastewater, which is provided on the basis of a large amount of research and engineering practice, and removes suspended matters in the wastewater through acidic filtration; removing metal ions by flocculation precipitation; then, substances such as fluorine, chlorine and the like are recovered through drying, and organic substances are removed; or recovering ammonia-containing by-products by a high-alkali ammonia removal process, and recovering substances such as fluorine, chlorine and the like by condensation crystallization. The method can effectively treat the acidic washing wastewater, realizes the reduction of heavy metal hazardous waste, clean treatment and recycling of ammonia nitrogen, and avoids the blockage of equipment by elemental sulfur, zero discharge of wastewater, low dust viscosity and no bag pasting phenomenon; the resources are recovered and reused, and the environment is protected.
In the process of treating multi-pollutant flue gas, the SRG gas of the active carbon is washed to remove impurities, and a large amount of acidic washing wastewater is generated. The components are complex, the wastewater is newly emerged, and no reference technology exists at home and abroad. Only the control technology of single pollutants exists, such as the ammonia nitrogen heavy metal composite wastewater treatment technology, but the problems of ammonia nitrogen volatilization, incomplete treatment and the like exist, and the problems of incomplete wastewater drying, easy bag pasting of crystallization products and the like exist in the flue gas waste heat drying wastewater. In addition, the current wastewater treatment process does not effectively control elemental sulfur, and the threat of elemental sulfur blocking equipment exists. The method determines a process route by analyzing the characteristics of the wastewater and the migration rule of pollutants, can realize the reduction of heavy metal hazardous waste, the clean treatment and recycling of ammonia nitrogen and the zero discharge of the wastewater, and avoids the blockage of equipment by elemental sulfur.
According to the first embodiment provided by the invention, a zero-emission treatment method for acidic flue gas washing wastewater is provided.
A zero discharge treatment method for acidic flue gas washing wastewater comprises the following steps:
1) and (3) wet washing: washing the acidic flue gas by a wet method through a wet method washing device to obtain acidic flue gas washing wastewater;
2) acid filtration: carrying out acidic filtration on the acidic flue gas washing wastewater by an acidic filtration device to obtain suspended substance precipitate and clear liquid;
3) clear liquid flocculation: introducing the clear liquid obtained in the step 2) into a flocculation precipitation device, and adding mixed alkali to flocculate and precipitate the clear liquid to obtain metal-containing sludge and salt-containing wastewater;
4) treating salt-containing wastewater: treating the salt-containing wastewater obtained in the step 3) by the following steps:
4a) mixing the salt-containing wastewater with alkali liquor, atomizing by an atomizer, conveying to a flue gas pipeline, drying by flue gas in the flue gas pipeline, and dedusting by a deduster to obtain crystallized salt and ammonia-containing flue gas.
According to a second embodiment provided by the invention, a zero-emission treatment method for acidic flue gas washing wastewater is provided.
A zero discharge treatment method for acidic flue gas washing wastewater comprises the following steps:
1) and (3) wet washing: washing the acidic flue gas by a wet method through a wet method washing device to obtain acidic flue gas washing wastewater;
2) acid filtration: carrying out acidic filtration on the acidic flue gas washing wastewater by an acidic filtration device to obtain suspended substance precipitate and clear liquid;
3) clear liquid flocculation: introducing the clear liquid obtained in the step 2) into a flocculation precipitation device, and adding mixed alkali to flocculate and precipitate the clear liquid to obtain metal-containing sludge and salt-containing wastewater;
4) treating salt-containing wastewater: treating the salt-containing wastewater obtained in the step 3) by the following steps:
4b) carrying out ammonia removal treatment on the salt-containing wastewater by a high-alkali ammonia removal device to obtain an ammonia-containing byproduct and ammonia-removed wastewater; and then cooling and condensing the ammonia-removing wastewater by a condensing and crystallizing device to obtain crystallized salt and clean water.
Preferably, the method further comprises: 5) metal recovery: and (3) passing the metal-containing sludge obtained in the step 3) through a metal recovery device to recover metals.
Preferably, step 3) further comprises an oxidation step; the method specifically comprises the following steps: oxidizing the clear liquid obtained in the step 2) through an oxidation device, then introducing the oxidized clear liquid into a flocculation precipitation device, adding mixed alkali, and performing a weak alkali flocculation precipitation process to flocculate and precipitate the clear liquid to obtain the metal-containing sludge and salt-containing wastewater.
In the present invention, the oxidation treatment employs one or more of chemical oxidation, electrochemical oxidation, ultraviolet catalytic oxidation, air oxidation, or chemical oxidation.
Preferably, the clean water obtained in step 4b) is recycled to the wet scrubbing unit.
Preferably, the acid flue gas is SRG gas. The SRG gas is: the multi-pollutant flue gas is adsorbed by an adsorption tower, an adsorbent is arranged in the adsorption tower, and the adsorbent adsorbed with pollutants is obtained by analyzing through an analyzing tower.
Preferably, the adsorbent is solid or liquid, and more preferably, the adsorbent is one or more of activated carbon, molecular sieve, MOFs, ionic liquid and organic amine.
Preferably, the ammonia-containing flue gas obtained in step 4a) is sent to an adsorption tower for cyclic treatment.
Preferably, the suspension in step 2) is precipitated as carbon powder. Preferably, the carbon powder is used for synthesizing large-particle activated carbon and returns to the adsorption tower for recycling through a carbon powder recycling process.
In the present invention, in step 1), the solution used in the wet washing is an acidic solution (e.g., a 0.5-10% diluted hydrochloric acid or diluted sulfuric acid or diluted phosphoric acid solution). The concentration is, for example, 1 wt.%, 4 wt.%, 5 wt.% or 7 wt.%.
Preferably, the pH value of the acidic solution is 0 to 7, preferably 1 to 6, and more preferably 2 to 5.
Preferably, the solution is dilute sulfuric acid or dilute hydrochloric acid or dilute phosphoric acid.
Preferably, in the wet washing process, the volume flow ratio of the SRG gas to the acidic solution is 1: 10-100, preferably 1: 20-80, and more preferably 1: 30-60.
In the invention, in the step 2), the acidic filtration is specifically as follows: the suspended matters are removed by utilizing the self gravity settling action or the interception action of a filter. The concentration of suspended matters in the clear liquid after acidic filtration is 0-100 mg/L, preferably 1-80 mg/L, and more preferably 2-50 mg/L.
In the invention, the acidic flue gas washing wastewater comprises one or more of suspended matters, metal ions, ammonia nitrogen, fluorine and chlorine and organic pollutants. Preferably, the metal ions are one or more of iron, copper, lead, calcium, zinc, cadmium, cobalt, nickel and aluminum.
In the invention, in the step 3), the flocculation precipitation is specifically as follows: adding mixed alkali into the clear liquid, adjusting the pH value to be alkalescent, and flocculating and precipitating the clear liquid with weak alkali to obtain metal-containing sludge and salt-containing wastewater.
Preferably, the pH of the serum is adjusted to 7-10, preferably 7.2-9, more preferably 7.5-8.5.
Preferably, the mixed alkali is a mixture of soluble hydroxide and soluble carbonate, or a mixture of soluble hydroxide and soluble bicarbonate; more preferably, the mixed alkali is a mixture of one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide and one or more of sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate.
In the present invention, in step 4a), the atomization is specifically: and dispersing the mixture of the clear liquid and the alkali liquor into small fog drops through an atomizer, wherein the particle size of the small fog drops is 10-100 microns, preferably 15-80 microns, and more preferably 20-50 microns.
Preferably, the alkali liquor is one or more of soluble hydroxide, soluble carbonate and soluble bicarbonate, and is preferably sodium hydroxide.
Preferably, the addition amount of the alkali liquor is 0 to 0.5 times, preferably 0.01 to 0.25 times, and more preferably 0.05 to 0.1 times of the amount of the clear liquor.
In the present invention, the dust removal treatment in step 4a) employs dry dust removal. Preferably, electric dust removal, cloth bag dust removal or ceramic dust removal, and preferably cloth bag dust removal.
In the present invention, after the dust removal treatment, the crystallized salt is discharged from the solid outlet of the dust remover.
In the present invention, in step 4b), the ammonia removal treatment specifically comprises: adding strong base into the salt-containing wastewater obtained in the step 3); adjusting the pH value of the salt-containing wastewater to 10-14, preferably 10.5-13.5, more preferably 11-13; separating and recovering ammonia to obtain ammonia-containing by-product and ammonia-removing waste water.
Preferably, the separation adopts one or more of blowing ammonia removal, membrane separation and ammonia removal by evaporation.
Preferably, the strong base is one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide.
In the invention, in the step 4b), the cooling and condensing treatment specifically comprises: and adjusting the temperature of the ammonia removal wastewater to low temperature, and condensing and crystallizing the salt in the ammonia removal wastewater to obtain crystallized salt and clean water.
Preferably, the low temperature is 0 to 30 ℃, preferably 5 to 25 ℃, more preferably 10 to 20 ℃.
Preferably, the crystalline salt is one or more of sulfate, chloride and fluoride.
In the invention, the multi-pollutant flue gas is SO2And one or more of NOx, dust, VOCs and heavy metals.
In the invention, the multi-pollutant flue gas is derived from complex gas containing sulfur dioxide generated in the steel, electric, colored, petrochemical, chemical or building material industries.
Preferably, the volume content of sulfur dioxide in the multi-pollutant flue gas is 0.01-1%, preferably 0.03-0.8%, and more preferably 0.05-0.5%.
Preferably, the temperature of the multi-pollutant flue gas is 100-200 ℃, preferably 120-180 ℃, and more preferably 130-160 ℃.
According to the third embodiment provided by the invention, a zero-emission treatment device for acidic flue gas washing wastewater is provided.
An acid flue gas washing wastewater zero emission treatment device or a device used for the method in the first or second embodiment comprises a wet washing device, an acid filtering device, a flocculation precipitation device, an atomizer, a flue gas pipeline and a dust remover. And conveying the acidic flue gas to a feed inlet of a wet scrubbing device. And a liquid outlet of the wet washing device is connected with the acid filtering device. The liquid outlet of the acid filtering device is connected to the flocculation precipitation device. The liquid outlet of the flocculation precipitation device is connected to the atomizer. The atomizer is connected to the flue gas duct. The flue gas pipeline is connected to the dust remover.
According to a fourth embodiment provided by the invention, a zero-emission treatment device for acidic flue gas washing wastewater is provided.
The utility model provides an acid flue gas washing waste water zero release processing apparatus, the device includes wet process washing device, acid filter equipment, flocculation and precipitation device, high-alkali ammonia removal device and condensation crystallization device. And conveying the acidic flue gas to a feed inlet of a wet scrubbing device. And a liquid outlet of the wet washing device is connected with the acid filtering device. The liquid outlet of the acid filtering device is connected to the flocculation precipitation device. The liquid outlet of the flocculation precipitation device is connected to a high-alkali ammonia removal device. And a liquid outlet of the high-alkali ammonia removal device is connected to the condensation crystallization device.
Preferably, the apparatus comprises an oxidation apparatus, an adsorption column and a desorption column. And conveying the multi-pollutant flue gas to the adsorption tower through a flue gas conveying pipeline. The adsorbent outlet of the adsorption tower is connected to the desorption tower. And an SRG gas outlet of the desorption tower is connected to a feed inlet of the wet scrubbing device through a pipeline. And a liquid outlet of the wet washing device is connected with the acid filtering device. The liquid outlet of the acid filtration device is connected to the oxidation device. The outlet of the oxidation device is connected to the flocculation precipitation device.
Preferably, the apparatus comprises a metal recovery apparatus. The solid outlet of the flocculation precipitation device is connected to a metal recovery device.
Preferably, the solids outlet of the acidic filtration device is connected to the adsorbent inlet of the adsorption column. And a clean water outlet of the condensation crystallization device 7 is connected to a wet washing device.
Preferably, the atomizer is provided with an alkali liquor inlet. The gas outlet of the dust remover is connected to the gas inlet of the adsorption tower.
In the invention, 1) acidic flue gas washing wastewater is subjected to acidic filtration to obtain suspended substance precipitate and clear liquid; 2) adding mixed alkali into the filtered supernatant, adjusting the pH value of the wastewater to be alkalescent, and forming a precipitate by metal ions; filtering to obtain filter residue containing metal ion precipitate and salt-containing wastewater; 3) salt-containing wastewater is added into a bypass flue through an atomizer, drying crystallization is realized by using the waste heat of flue gas, and simultaneously, a certain amount of alkali liquor is added into the atomizer to adjust the fog drops of the wastewater to be high-alkalinity; 4) and recovering the crystallized salt generated after drying by using a dust remover, and discharging the crystallized salt from the system.
In the invention, 1) acidic flue gas washing wastewater is subjected to acidic filtration to obtain suspended substance precipitate and clear liquid; 2) adding mixed alkali into the filtered supernatant, adjusting the pH value of the wastewater to be alkalescent, and forming a precipitate by metal ions; filtering to obtain filter residue containing metal ion precipitate and salt-containing wastewater; 3) removing ammonia by a high-alkali ammonia removal device to obtain an ammonia-containing byproduct and ammonia-removal wastewater; 4) and then cooling and condensing the ammonia-removing wastewater by a condensing and crystallizing device to obtain crystallized salt and clean water.
The technical principle of the process is as follows:
1) acid precipitation/acid filtration: the nature that the suspended matter is easy to settle is utilized, and the suspended matter is filtered in the acidity by the gravity action and the acidic filter under the acidic condition.
2) Flocculation and weak base precipitation: adjusting the wastewater to be alkalescent by adopting mixed alkali, wherein the pH value is less than or equal to 10; the metal cation will react with OH-、CO3 2-Or HCO3 -And the like, to form insoluble substances. And the precipitate is settled by adding a flocculating agent, so that the metal cations in the wastewater are removed, and the hardness of the wastewater is reduced.
3) Wastewater atomization and alkali adjustment: because the small liquid drops are easy to evaporate and dry, the waste water is atomized into 10-100 mu m particle size after being pressurized by an air compressor, and the drying speed of the waste water is improved. Meanwhile, ammonia is easy to escape from the wastewater under high alkali, so that the workshop environment is worsened and the recovery rate of ammonia nitrogen is low. The purpose of adopting atomization alkali regulation is to quickly regulate the pH value of small drops of atomized wastewater to be more than or equal to 10 in a closed space, realize the conversion of ammonia nitrogen into free ammonia and simultaneously avoid ammonia escape caused by open alkali regulation.
4) And (3) crystal recovery: after the solution is evaporated, the solid mainly comprises sulfate, chloride and fluoride salt, is conventional inorganic salt, and can be recovered and removed by adopting a dust removal material with the filter diameter of less than 1 mu m. Commonly used dust removal materials include cloth bags, ceramics, metal membranes, and the like. After the suspended matters in the wastewater are removed by acidic filtration, the wastewater is changed into small-particle acidic fog drops by an atomizer, and the acidic fog drops are in contact with atomized alkali liquor quickly and have neutralization reaction to form alkaline liquid drops due to small particle size, large specific surface area and high mass transfer rate, and the dry crystallization is realized by quickly absorbing the heat of the flue gas. Because the heavy metal is removed by the weak base flocculation precipitation, the dried crystallized salt does not contain the heavy metal, the harmfulness of the crystallized salt is reduced, and the harmless treatment of fluorine and chlorine is realized.
5) Carbon powder recycling: a large amount of activated carbon powder is generated in the processes of activated carbon adsorption and desorption due to chemical loss and mechanical loss, a part of the carbon powder is separated after being screened with the desorbed activated carbon, and a part of the carbon powder enters the wastewater with the desorbed gas. Based on the particle size analysis and the surface hydrophobic characteristic of the carbon powder, the method filters the carbon powder in the wastewater under the acidic condition by reasonably designing the filtering condition, and mixes the carbon powder with the carbon powder under the sieve after drying, so that the carbon powder is granulated, combusted and buried, the resource utilization of the carbon powder is realized, and the operation cost is reduced.
6) Ammonia nitrogen clean recovery: after ammonia enters flue gas, part of ammonia and SO2The binding becomes ammonium sulfite and a portion reacts with NOx in an SCR reaction to form nitrogen. Because the ammonium sulfite is unstable, the generated ammonium sulfite is easily decomposed into ammonia gas and SO in the high-temperature regeneration process of the active carbon2. Since ammonia is very soluble in water, almost all ammonia enters the washing wastewater. The invention adopts the technologies that heavy metals are precipitated by mixed alkali in weak alkali (7-9) and ammonia is removed or recovered by high alkali (11-14), can effectively avoid ammonia gas escape and form a metal ammonia nitrogen stable complex compound when heavy metals are precipitated by high alkali, and realizes the clean recovery or treatment of ammonia nitrogen.
7) Harmlessness of fluorine and chlorine: fluorine and chlorine in the flue gas are easily adsorbed by the activated carbon, and then desorbed at high temperature and enter the washing wastewater. Because the solubility of the fluorine chloride salt in water is reduced along with the reduction of the temperature, the method adopts the reduction of the solution temperature to separate out the fluorine chloride salt crystals after the heavy metal and ammonia nitrogen in the wastewater are removed. The problems of co-precipitation with heavy metals and difficult crystallization of ammonium salt are avoided, the harmfulness of the crystallized salt is reduced, and harmless treatment of fluorine and chlorine is realized.
In the invention, after wet washing, the generated acidic washing wastewater comprises carbon powder in a suspended state and a wastewater solution containing metal ions; the part of the acidic washing wastewater is subjected to acidic filtration to separate suspended matters (such as carbon powder) in the wastewater to obtain carbon powder, and the part of the carbon powder can be recycled through a carbon powder recycling process, for example, a re-granulation process is adopted to obtain large-particle activated carbon, and then the large-particle activated carbon is recycled to an adsorption tower. The wastewater after the suspended matter is separated contains metal ions (or metal salts) which are clear liquid; and (3) subjecting the clear liquid to a flocculation precipitation process, adding mixed alkali into the clear liquid to enable most heavy metal ions in the clear liquid to form precipitates, introducing the precipitates into the metal-containing sludge, and then recovering metals from the metal-containing sludge to obtain a pure metal recovered material which can be sold or used for other purposes. The salt-containing wastewater obtained after the flocculation and precipitation process is characterized in that an alkali solution is added into the salt-containing wastewater, after atomization, heat emitted by a flue gas conveying pipeline is used for drying, metal ions which are not precipitated in the flocculation and precipitation process are crystallized in the salt-containing wastewater after drying, and chloride ions, fluoride ions, sulfate ions and the like in the wastewater are dried by adding the alkali solution into the salt-containing wastewater to form a clear solution and heat emitted by an alkali solution mixture through the flue gas conveying pipeline, and water is volatilized to form crystallized salt. The volatile matter is pollution-free matter. The crystalline salt can be sold or used for other purposes, resulting in economic value. The crystal salt is sulfate, chloride or fluoride.
In a second embodiment of the present invention, after washing by a wet method, the generated acidic washing wastewater comprises carbon powder, metal ions in a suspended state; the part of the acidic washing wastewater is subjected to acidic filtration to separate suspended matters (namely carbon powder) in the wastewater to obtain carbon powder, and the part of the carbon powder can be recycled through a carbon powder recycling process, for example, a re-granulation process is adopted to obtain large-particle activated carbon, and then the large-particle activated carbon is recycled to an adsorption tower. The wastewater after the suspended matter is separated contains metal ions (or metal salts) which are clear liquid; removing COD in the clear liquid after the acid washing through an oxidation process, so that organic matter components in the clear liquid are greatly reduced; heavy metal ions are removed from the sludge through flocculation precipitation, and the metal ions enter the metal-containing sludge, and then are collected and enriched through a metal recovery process, and are sold or used for other purposes. Removing ammonia in the salt-containing wastewater after the flocculation precipitation procedure through a high-alkali ammonia removal process to obtain an ammonia-containing byproduct and ammonia-removed wastewater; the ammonia-containing by-product can be directly sold, and economic value is generated. Removing chloride ions, fluoride ions, sulfate ions and the like from the ammonia-removing wastewater through condensation and crystallization; obtaining crystal salt and clean water; the crystal salt is sulfate, chloride or fluoride. The crystallized salt can be sold directly, resulting in economic value. The rest of crystallization process water is recycled to the wet washing procedure and can be recycled.
By adopting the method, after the multi-pollutant smoke is treated by the activated carbon, the activated carbon can be completely recycled. The sulfides in the contaminants are recovered as sulfur-containing by-products. Most of the metal ions can be recovered by the flocculation precipitation step and the metal recovery step, and the remaining chloride ions, fluoride ions, sulfate ions, and the like are converted into crystal salts. Therefore, the synergistic treatment of the multi-pollutant flue gas is really realized, the zero discharge of waste water is realized, the secondary pollution is not generated, and metal ions (or heavy metal ions) in the multi-pollutant flue gas are recovered. Changing waste into valuable, recycling, saving cost, recycling resources and protecting environment.
In the invention, the SRG gas refers to the enriched flue gas discharged after being analyzed by the desorption tower. The SRG gas (or SRG flue gas) has high temperature, high dust content and SO2High content, high water content, complex smoke impurity components and the like. In the art, SRG gas is also referred to simply as sulfur-rich gas; used for being conveyed to an acid making system for making acid.
Compared with the prior art, the method has the following beneficial technical effects:
(1) the method of the invention treats the washing wastewater of the acid-washing flue gas, and prevents carbon powder from being blocked by acidic filtration; preventing the sulfur colloid from dissolving to form sodium thiosulfate and decomposing during drying;
(2) the acid filtered clear liquid is subjected to a flocculation precipitation process, so that heavy metals form heavy metal precipitates, the heavy metals are prevented from entering crystallized salt, and hazardous waste reduction is realized; meanwhile, mixed alkali is adopted in the flocculation precipitation process, so that a weak alkali environment is ensured, and ammonia volatilization and formation of a metal ammonia nitrogen complex are avoided;
(3) the ammonia-containing wastewater in the flocculation precipitation process passes through an atomizer and is dried by using the waste heat of the flue gas in a flue; high-alkali atomization is adopted, which is beneficial to recycling ammonia gas; alkaline drying to prevent formation of high viscosity ammonium bisulfate and other by-products;
(4) the invention adopts the technologies that heavy metals are precipitated by mixed alkali in weak alkali (7-9) and ammonia is removed or recovered by high alkali (11-14), can effectively avoid ammonia gas escape and form a metal ammonia nitrogen stable complex compound when heavy metals are precipitated by high alkali, and realizes the clean recovery or treatment of ammonia nitrogen.
(5) Because the solubility of the fluorine chloride salt in water is reduced along with the reduction of the temperature, the method adopts the reduction of the solution temperature to separate out the fluorine chloride salt crystals after the heavy metal and ammonia nitrogen in the wastewater are removed. The problems of co-precipitation with heavy metals and difficult crystallization of ammonium salt are avoided, the harmfulness of the crystallized salt is reduced, and harmless treatment of fluorine and chlorine is realized.
Drawings
FIG. 1 is a process flow diagram of a zero discharge treatment method for acidic flue gas washing wastewater according to the present invention;
FIG. 2 is a process flow diagram of a second method for zero-discharge treatment of acidic flue gas washing wastewater in accordance with the present invention;
FIG. 3 is a process flow diagram of a third method for zero-discharge treatment of acidic flue gas washing wastewater according to the present invention;
FIG. 4 is a schematic structural diagram of a zero-discharge treatment device for acidic flue gas washing wastewater, according to the present invention;
FIG. 5 is a schematic structural diagram of a second device for zero-discharge treatment of acidic flue gas washing wastewater according to the invention.
Reference numerals: 1: a wet scrubbing apparatus; 2: an acidic filtration unit; 3: a flocculation precipitation device; 4: an atomizer; 5: a dust remover; 6: a high-alkali ammonia removal device; 7: a condensation crystallization device; 8: a metal recovery device; 9: an oxidation unit; 10: an adsorption tower; 11: a resolution tower; l1: a flue gas duct.
Detailed description of the preferred embodiments
According to the first embodiment provided by the invention, a zero-emission treatment method for acidic flue gas washing wastewater is provided.
A zero discharge treatment method for acidic flue gas washing wastewater comprises the following steps:
1) and (3) wet washing: washing the acidic flue gas by a wet method through a wet method washing device 1 to obtain acidic flue gas washing wastewater;
2) acid filtration: carrying out acidic filtration on the acidic flue gas washing wastewater through an acidic filtration device 2 to obtain suspended matter precipitate and clear liquid;
3) clear liquid flocculation: introducing the clear liquid obtained in the step 2) into a flocculation precipitation device 3, and adding mixed alkali to flocculate and precipitate the clear liquid to obtain metal-containing sludge and salt-containing wastewater;
4) treating salt-containing wastewater: treating the salt-containing wastewater obtained in the step 3) by the following steps:
4a) mixing the salt-containing wastewater with alkali liquor, atomizing by an atomizer 4, conveying to a flue gas pipeline L1, drying by flue gas in the flue gas pipeline, and performing dust removal treatment by a dust remover 5 to obtain crystallized salt and ammonia-containing flue gas.
According to a second embodiment provided by the invention, a zero-emission treatment method for acidic flue gas washing wastewater is provided.
A zero discharge treatment method for acidic flue gas washing wastewater comprises the following steps:
1) and (3) wet washing: washing the acidic flue gas by a wet method through a wet method washing device 1 to obtain acidic flue gas washing wastewater;
2) acid filtration: carrying out acidic filtration on the acidic flue gas washing wastewater through an acidic filtration device 2 to obtain suspended matter precipitate and clear liquid;
3) clear liquid flocculation: introducing the clear liquid obtained in the step 2) into a flocculation precipitation device 3, and adding mixed alkali to flocculate and precipitate the clear liquid to obtain metal-containing sludge and salt-containing wastewater;
4) treating salt-containing wastewater: treating the salt-containing wastewater obtained in the step 3) by the following steps:
4b) the salt-containing wastewater is subjected to ammonia removal treatment by a high-alkali ammonia removal device 6 to obtain an ammonia-containing byproduct and ammonia-removed wastewater; then the ammonia-removing wastewater is cooled and condensed by a condensation crystallization device 7 to obtain crystallized salt and clean water.
Preferably, the method further comprises: 5) metal recovery: the metal-containing sludge obtained in the step 3) is passed through a metal recovery device 8 to recover metals.
Preferably, step 3) further comprises an oxidation step; the method specifically comprises the following steps: oxidizing the clear liquid obtained in the step 2) by an oxidation device 9, then introducing the oxidized clear liquid into a flocculation precipitation device 3, adding mixed alkali, and performing a weak alkali flocculation precipitation process to flocculate and precipitate the clear liquid to obtain the metal-containing sludge and the salt-containing wastewater.
In the present invention, the oxidation treatment employs one or more of chemical oxidation, electrochemical oxidation, ultraviolet catalytic oxidation, air oxidation, or chemical oxidation.
Preferably, the clean water obtained in step 4b) is recycled to the wet scrubbing apparatus 1.
Preferably, the acid flue gas is SRG gas. The SRG gas is: the multi-pollutant flue gas is adsorbed by an adsorption tower 10, an adsorbent is arranged in the adsorption tower 10, and the adsorbent adsorbed with pollutants is obtained by analyzing through an analyzing tower 11.
Preferably, the adsorbent is solid or liquid, and more preferably, the adsorbent is one or more of activated carbon, molecular sieve, MOFs, ionic liquid and organic amine.
Preferably, the ammonia-containing flue gas obtained in step 4a) is sent to an adsorption column 10 for cyclic treatment.
Preferably, the suspension in step 2) is precipitated as carbon powder. Preferably, the carbon powder is used for synthesizing large-particle activated carbon and is returned to the adsorption tower 10) for recycling through the carbon powder recycling process.
In the present invention, in step 1), the solution used in the wet washing is an acidic solution (e.g., a 0.5-10% diluted hydrochloric acid or diluted sulfuric acid or diluted phosphoric acid solution). The concentration is, for example, 1 wt.%, 4 wt.%, 5 wt.% or 7 wt.%.
Preferably, the pH value of the acidic solution is 0 to 7, preferably 1 to 6, and more preferably 2 to 5.
Preferably, the solution is dilute sulfuric acid or dilute hydrochloric acid or dilute phosphoric acid solution.
Preferably, in the wet washing process, the volume flow ratio of the SRG gas to the solution is 1: 10-100, preferably 1: 20-80, and more preferably 1: 30-60.
In the invention, in the step 2), the acidic filtration is specifically as follows: the suspended matters are removed by utilizing the self gravity settling action or the interception action of a filter. The concentration of suspended matters in the clear liquid after acidic filtration is 0-100 mg/L, preferably 1-80 mg/L, and more preferably 2-50 mg/L.
In the invention, the acidic flue gas washing wastewater comprises one or more of suspended matters, metal ions, ammonia nitrogen, fluorine and chlorine and organic pollutants. Preferably, the metal ions are one or more of iron, copper, lead, calcium, zinc, cadmium, cobalt, nickel and aluminum.
In the invention, in the step 3), the flocculation precipitation is specifically as follows: adding mixed alkali into the clear liquid, adjusting the pH value to be alkalescent, and flocculating and precipitating the clear liquid with weak alkali to obtain metal-containing sludge and salt-containing wastewater.
Preferably, the pH of the serum is adjusted to 7-10, preferably 7.2-9, more preferably 7.5-8.5.
Preferably, the mixed alkali is a mixture of soluble hydroxide and soluble carbonate, or a mixture of soluble hydroxide and soluble bicarbonate; more preferably, the mixed alkali is a mixture of one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide and one or more of sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate.
In the present invention, in step 4a), the atomization is specifically: and dispersing the mixture of the clear liquid and the alkali liquor into small fog drops through an atomizer, wherein the particle size of the small fog drops is 10-100 microns, preferably 15-80 microns, and more preferably 20-50 microns.
Preferably, the alkali liquor is one or more of soluble hydroxide, soluble carbonate and soluble bicarbonate, and is preferably sodium hydroxide.
Preferably, the addition amount of the alkali liquor is 0 to 0.5 times, preferably 0.01 to 0.25 times, and more preferably 0.05 to 0.1 times of the amount of the clear liquor.
In the present invention, the dust removal treatment in step 4a) employs dry dust removal. Preferably, electric dust removal, cloth bag dust removal or ceramic dust removal, and preferably cloth bag dust removal.
In the present invention, after the dust-removing treatment, the crystallized salt is discharged from the solid outlet of the dust remover 5.
In the present invention, in step 4b), the ammonia removal treatment specifically comprises: adding strong base into the salt-containing wastewater obtained in the step 3); adjusting the pH value of the salt-containing wastewater to 10-14, preferably 10.5-13.5, more preferably 11-13; separating and recovering ammonia to obtain ammonia-containing by-product and ammonia-removing waste water.
Preferably, the separation adopts one or more of blowing ammonia removal, membrane separation and ammonia removal by evaporation.
Preferably, the strong base is one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide.
In the invention, in the step 4b), the cooling and condensing treatment specifically comprises: and adjusting the temperature of the ammonia removal wastewater to low temperature, and condensing and crystallizing the salt in the ammonia removal wastewater to obtain crystallized salt and clean water.
Preferably, the low temperature is 0 to 30 ℃, preferably 5 to 25 ℃, more preferably 10 to 20 ℃.
Preferably, the crystalline salt is one or more of sulfate, chloride and fluoride.
In the invention, the multi-pollutant flue gas is SO2And one or more of NOx, dust, VOCs and heavy metals.
In the invention, the multi-pollutant flue gas is derived from complex gas containing sulfur dioxide generated in the steel, electric, colored, petrochemical, chemical or building material industries.
Preferably, the volume content of sulfur dioxide in the multi-pollutant flue gas is 0.01-1%, preferably 0.03-0.8%, and more preferably 0.05-0.5%.
Preferably, the temperature of the multi-pollutant flue gas is 100-200 ℃, preferably 120-180 ℃, and more preferably 130-160 ℃.
According to the third embodiment provided by the invention, a zero-emission treatment device for acidic flue gas washing wastewater is provided.
An acid flue gas washing wastewater zero emission treatment device or a device used for the method in the first or second embodiment comprises a wet washing device 1, an acid filtering device 2, a flocculation precipitation device 3, an atomizer 4, a flue gas pipeline L1 and a dust remover 5. The acidic flue gas is conveyed to a feed inlet of the wet scrubbing device 1. The liquid outlet of the wet-method washing device 1 is connected with the acid filtering device 2. The liquid outlet of the acid filtration device 2 is connected to a flocculation and precipitation device 3. The liquid outlet of the flocculation and precipitation device 3 is connected to the atomizer 4. The atomizer 4 is connected to a flue gas duct L1. The flue gas duct L1 is connected to the dust separator 5.
According to a fourth embodiment provided by the invention, a zero-emission treatment device for acidic flue gas washing wastewater is provided.
The utility model provides an acid flue gas washing waste water zero release processing apparatus, the device includes wet process washing device 1, acid filter equipment 2, flocculation and precipitation device 3, high-alkali ammonia removal device 6 and condensation crystallization device 7. The acidic flue gas is conveyed to a feed inlet of the wet scrubbing device 1. The liquid outlet of the wet-method washing device 1 is connected with the acid filtering device 2. The liquid outlet of the acid filtration device 2 is connected to a flocculation and precipitation device 3. The liquid outlet of the flocculation precipitation device 3 is connected to a high-alkali ammonia removal device 6. The liquid outlet of the high-alkali ammonia removal device 6 is connected to a condensation crystallization device 7.
Preferably, the apparatus includes an oxidation apparatus 9, an adsorption column 10, and a desorption column 11. The multi-pollutant flue gas is conveyed to the adsorption tower 10 through a flue gas conveying pipeline L1. The adsorbent outlet of the adsorption column 10 is connected to a desorption column 11. The SRG gas outlet of the stripper column 11 is connected to the feed inlet of the wet scrubbing apparatus 1 via a pipe. The liquid outlet of the wet-method washing device 1 is connected with the acid filtering device 2. The liquid outlet of the acid filter unit 2 is connected to an oxidation unit 9. The outlet of the oxidation device 9 is connected to the flocculation and sedimentation device 3.
Preferably, the apparatus includes a metal recovery apparatus 8. The solids outlet of the flocculation and precipitation unit 3 is connected to a metal recovery unit 8.
Preferably, the solids outlet of the acidic filtration device 2 is connected to the adsorbent inlet of the adsorption column 10. The clean water outlet of the condensation crystallization device 7 is connected to the wet scrubbing device 1.
Preferably, the atomizer 4 is provided with an alkali liquor inlet. The gas outlet of the dust separator 5 is connected to the gas inlet of the adsorption tower 10.
Example 1
As shown in fig. 4, an acid flue gas washing wastewater zero discharge treatment device or a device used in the method described in the first or second embodiment comprises a wet washing device 1, an acid filtering device 2, a flocculation precipitation device 3, an atomizer 4, a flue gas pipeline L1 and a dust remover 5. The acidic flue gas is conveyed to a feed inlet of the wet scrubbing device 1. The liquid outlet of the wet-method washing device 1 is connected with the acid filtering device 2. The liquid outlet of the acid filtration device 2 is connected to a flocculation and precipitation device 3. The liquid outlet of the flocculation and precipitation device 3 is connected to the atomizer 4. The atomizer 4 is connected to a flue gas duct L1. The flue gas duct L1 is connected to the dust separator 5.
Example 2
Example 1 was repeated except that the apparatus included the oxidation apparatus 9, the adsorption column 10 and the desorption column 11. The multi-pollutant flue gas is conveyed to the adsorption tower 10 through a flue gas conveying pipeline L1. The adsorbent outlet of the adsorption column 10 is connected to a desorption column 11. The SRG gas outlet of the stripper column 11 is connected to the feed inlet of the wet scrubbing apparatus 1 via a pipe. The liquid outlet of the wet-method washing device 1 is connected with the acid filtering device 2. The liquid outlet of the acid filter unit 2 is connected to an oxidation unit 9. The outlet of the oxidation device 9 is connected to the flocculation and sedimentation device 3. The apparatus includes a metal recovery device 8. The solids outlet of the flocculation and precipitation unit 3 is connected to a metal recovery unit 8. The solids outlet of the acid filtration unit 2 is connected to the adsorbent inlet of the adsorption column 10. The clean water outlet of the condensation crystallization device 7 is connected to the wet scrubbing device 1. The atomizer 4 is provided with an alkali liquor inlet. The gas outlet of the dust separator 5 is connected to the gas inlet of the adsorption tower 10.
Example 3
As shown in fig. 5, the device for zero discharge treatment of acidic flue gas washing wastewater comprises a wet washing device 1, an acidic filtering device 2, a flocculation precipitation device 3, a high-alkali ammonia removal device 6 and a condensation crystallization device 7. The acidic flue gas is conveyed to a feed inlet of the wet scrubbing device 1. The liquid outlet of the wet-method washing device 1 is connected with the acid filtering device 2. The liquid outlet of the acid filtration device 2 is connected to a flocculation and precipitation device 3. The liquid outlet of the flocculation precipitation device 3 is connected to a high-alkali ammonia removal device 6. The liquid outlet of the high-alkali ammonia removal device 6 is connected to a condensation crystallization device 7.
Example 4
As shown in fig. 1, a zero-emission treatment method for acidic flue gas washing wastewater comprises the following steps:
1) and (3) wet washing: the acid flue gas is washed by a wet method through a wet method washing device 1, wherein the solution adopted by the wet method washing is an acid solution (namely dilute sulfuric acid), and the pH value is 4; obtaining acid flue gas washing wastewater;
2) acid filtration: carrying out acidic filtration on the acidic flue gas washing wastewater through an acidic filtration device 2, and removing suspended matters by utilizing the self gravity settling action or the filter interception action of the suspended matters; obtaining suspended matter precipitate and clear liquid;
3) clear liquid flocculation: introducing the clear liquid obtained in the step 2) into a flocculation precipitation device 3, adding sodium hydroxide and sodium carbonate, and adjusting the pH value to 8; flocculating and precipitating the clear liquid to obtain metal-containing sludge and salt-containing wastewater;
4) treating salt-containing wastewater: treating the salt-containing wastewater obtained in the step 3) by the following steps:
4a) mixing the salt-containing wastewater with sodium hydroxide, atomizing by an atomizer 4, conveying to a flue gas pipeline L1, drying by flue gas in the flue gas pipeline, and performing dust removal treatment by a dust remover 5 through cloth bag dust removal to obtain crystalline salt and ammonia-containing flue gas.
In this example, the concentration of the suspension in the supernatant after acidic filtration was 1 mg/L. And removing heavy metal ions in the clear liquid after the acid washing through flocculation and precipitation, wherein the metal ions enter the metal-containing sludge. And drying the salt-containing wastewater through a flue gas pipeline to obtain crystalline salt. Realizing zero discharge of waste water.
Example 5
As shown in fig. 2, a zero-emission treatment method for acidic flue gas washing wastewater comprises the following steps:
1) and (3) wet washing: the acid flue gas is washed by a wet method through a wet method washing device 1, wherein the solution adopted by the wet method washing is an acid solution (namely dilute hydrochloric acid), and the pH value is 4; obtaining acid flue gas washing wastewater;
2) acid filtration: carrying out acidic filtration on the acidic flue gas washing wastewater through an acidic filtration device 2, and removing suspended matters by utilizing the self gravity settling action or the filter interception action of the suspended matters; obtaining suspended matter precipitate and clear liquid;
3) clear liquid flocculation: introducing the clear liquid obtained in the step 2) into a flocculation precipitation device 3, adding potassium hydroxide and potassium bicarbonate, and adjusting the pH value to 8; flocculating and precipitating the clear liquid to obtain metal-containing sludge and salt-containing wastewater;
4) treating salt-containing wastewater: treating the salt-containing wastewater obtained in the step 3) by the following steps:
4b) adding sodium hydroxide into the salt-containing wastewater obtained in the step 3); adjusting the pH value of the salt-containing wastewater to 12; separating and recovering ammonia to obtain ammonia-containing by-product and ammonia-removing waste water. The separation is membrane separation. And then adjusting the temperature of the ammonia removal wastewater to 15 ℃, and condensing and crystallizing the salt in the ammonia removal wastewater to obtain crystallized salt and clean water. The crystal salt is sulfate, chloride or fluoride.
In this example, the concentration of the suspension in the supernatant after acidic filtration was 1 mg/L. And removing heavy metal ions in the clear liquid after the acid washing through flocculation and precipitation, wherein the metal ions enter the metal-containing sludge. Removing ammonia in the salt-containing wastewater after the flocculation precipitation procedure by a high-alkali ammonia removal process to obtain an ammonia-containing byproduct and ammonia-removed wastewater; the ammonia-containing by-product can be directly sold, and economic value is generated. Removing chloride ions and fluoride ions from the ammonia-removing wastewater through condensation and crystallization; obtaining crystal salt and clean water; the crystal salt is sulfate, chloride or fluoride. The crystallized salt can be sold directly, resulting in economic value. Realizing zero discharge of waste water and waste gas.
Example 6
As shown in fig. 3, example 4 is repeated except that the step 3) further comprises an oxidation process; the method specifically comprises the following steps: oxidizing the clear liquid obtained in the step 2) by an oxidation device 9 through electrochemical oxidation, then introducing the oxidized clear liquid into a flocculation precipitation device 3, adding mixed alkali, and performing a weak alkali flocculation precipitation process to flocculate and precipitate the clear liquid to obtain the metal-containing sludge and the salt-containing wastewater. The method further comprises the following steps: 5) metal recovery: the metal-containing sludge obtained in the step 3) is passed through a metal recovery device 8 to recover metals. The ammonia-containing flue gas obtained in step 4a) is conveyed to an adsorption tower 10 for cyclic treatment.
In the embodiment, the clear liquid after acid washing is subjected to an oxidation process to remove COD in the clear liquid, so that organic matter components in the clear liquid are greatly reduced; then removing heavy metal ions in the waste water by flocculation precipitation. The metal-containing sludge is subjected to a metal recovery process to enrich and recover metals, so that economic value is directly generated. The ammonia-containing flue gas after drying treatment is circulated to an adsorption tower for treatment, and zero discharge of waste water and waste gas is realized.
Example 7
Example 5 was repeated except that step 3) further included an oxidation step; the method specifically comprises the following steps: oxidizing the clear liquid obtained in the step 2) by an oxidation device 9 through electrochemical oxidation, then introducing the oxidized clear liquid into a flocculation precipitation device 3, adding mixed alkali, and performing a weak alkali flocculation precipitation process to flocculate and precipitate the clear liquid to obtain the metal-containing sludge and the salt-containing wastewater. The method further comprises the following steps: 5) metal recovery: the metal-containing sludge obtained in the step 3) is passed through a metal recovery device 8 to recover metals. The clean water obtained in step 4b) is recycled to the wet scrubbing apparatus 1.
In the embodiment, the clear liquid after acid washing is subjected to an oxidation process to remove COD in the clear liquid, so that organic matter components in the clear liquid are greatly reduced; then removing heavy metal ions in the waste water by flocculation precipitation. The metal-containing sludge is subjected to a metal recovery process to enrich and recover metals, so that economic value is directly generated. Clean water generated after condensation and crystallization treatment is circulated to a wet washing device, so that the water resource is recycled.
Example 8
Example 6 was repeated, the acid flue gas being SRG gas. The multi-pollutant flue gas is adsorbed by an adsorption tower 10, active carbon is arranged in the adsorption tower 10, and the active carbon adsorbed with pollutants is obtained by analyzing through an analyzing tower 11. The suspended matters are precipitated into carbon powder in the step 2). The carbon powder is used for synthesizing large-particle activated carbon and returns to the adsorption tower 10) for recycling through a carbon powder recycling process (re-granulation). The SRG gas comprises suspended matters, metal ions, ammonia nitrogen, fluorine and chlorine and organic pollutants. The metal ions are iron, copper, lead, calcium, zinc, cadmium, cobalt, nickel and aluminum.
In the step 1), the volume flow ratio of the SRG gas to the solution in the wet washing process is 1: 45. In the step 2), the concentration of suspended matters in the clear liquid after acidic filtration is 1.8 mg/L. Through a flocculation precipitation process, the content of heavy metal ions in the salt-containing wastewater is 6.7 mg/L.
And (3) recovering sulfuric acid from high-sulfur gas generated in the SRG gas treatment process after a sulfur recycling process, and circulating the residual sulfur-containing tail gas to a flue gas conveying pipeline L1 for centralized treatment. The salt-containing wastewater after the flocculation precipitation process is changed into crystal salt through the processes of adding alkali, atomizing, drying, dedusting and the like, and the crystal salt can be directly sold, so that economic benefits are generated; and screening the activated carbon after thermal regeneration to obtain large-particle activated carbon and small-particle activated carbon. The embodiment completely realizes the advantages of the synergistic treatment of multi-pollutant flue gas and the effective control of secondary pollution. The method can well treat secondary pollutants, change waste into valuable, recycle, realize zero discharge of wastewater, save cost, recover resources and protect environment.
Example 9
Example 7 was repeated, the acid flue gas being SRG gas. The multi-pollutant flue gas is adsorbed by an adsorption tower 10, active carbon is arranged in the adsorption tower 10, and the active carbon adsorbed with pollutants is obtained by analyzing through an analyzing tower 11. The suspended matters are precipitated into carbon powder in the step 2). The carbon powder is used for synthesizing large-particle activated carbon through a carbon powder recycling process (re-granulation) and returns to the adsorption tower 10 for recycling. The SRG gas comprises suspended matters, metal ions, ammonia nitrogen, fluorine and chlorine and organic pollutants. The metal ions are iron, copper, lead, calcium, zinc, cadmium, cobalt, nickel and aluminum.
In the step 1), the volume flow ratio of the SRG gas to the acidic solution in the wet washing process is 1: 45. In the step 2), the concentration of suspended matters in the clear liquid after acidic filtration is 1.8 mg/L.
The high-sulfur gas generated in the SRG gas treatment process is subjected to a sulfur recycling process to recover sulfuric acid. Most heavy metal ions are recovered in the flocculation precipitation process, and ammonia in the salt-containing wastewater after the flocculation precipitation process is removed through a high-alkali ammonia removal process to obtain an ammonia-containing byproduct and ammonia-removed wastewater; the ammonia-containing by-product can be directly sold, and economic value is generated. Removing chloride ions and fluoride ions from the ammonia-removing wastewater through condensation and crystallization; obtaining crystal salt and clean water; the crystal salt is sulfate, chloride or fluoride. The crystallized salt can be sold directly, resulting in economic value.
Claims (46)
1. A zero discharge treatment method for acidic flue gas washing wastewater comprises the following steps:
1) and (3) wet washing: washing the acidic flue gas by a wet method through a wet method washing device (1) to obtain acidic flue gas washing wastewater;
2) acid filtration: carrying out acidic filtration on the acidic flue gas washing wastewater through an acidic filtration device (2) to obtain suspended substance precipitate and clear liquid; the acidic filtration is specifically as follows: removing the suspended matters by utilizing the self gravity settling effect or the filter interception effect of the suspended matters, wherein the concentration of the suspended matters in the clear liquid after the acidic filtration is 0-100 mg/L;
3) clear liquid flocculation: introducing the clear liquid obtained in the step 2) into a flocculation precipitation device (3), adding mixed alkali to flocculate and precipitate the clear liquid, and obtaining metal-containing sludge and salt-containing wastewater; the flocculation precipitation specifically comprises the following steps: adding mixed alkali into the clear liquid, and adjusting the pH value to 7-10 to enable the clear liquid to be subjected to weak alkali flocculation and precipitation so as to obtain metal-containing sludge and salt-containing wastewater; the mixed alkali is one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide, and is a mixture of one or more of sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate;
4) treating salt-containing wastewater: treating the salt-containing wastewater obtained in the step 3) by the following steps:
4a) mixing the salt-containing wastewater with alkali liquor, atomizing by an atomizer (4), conveying to a flue gas pipeline (L1), drying by flue gas in the flue gas pipeline, and performing dust removal treatment by a dust remover (5) to obtain crystallized salt and ammonia-containing flue gas; or
4b) The salt-containing wastewater is subjected to ammonia removal treatment by a high-alkali ammonia removal device (6) to obtain an ammonia-containing byproduct and ammonia removal wastewater; then, cooling and condensing the ammonia-removing wastewater by a condensing crystallization device (7) to obtain crystallized salt and clean water;
the step 3) also comprises an oxidation process; the method specifically comprises the following steps: oxidizing the clear liquid obtained in the step 2) through an oxidation device (9), then introducing the oxidized clear liquid into a flocculation precipitation device (3), adding mixed alkali, and performing a weak alkali flocculation precipitation process to flocculate and precipitate the clear liquid to obtain the metal-containing sludge and the salt-containing wastewater.
2. The method of claim 1, wherein: the method further comprises the following steps: 5) metal recovery: the metal-containing sludge obtained in the step 3) passes through a metal recovery device (8) to recover metals.
3. The method of claim 2, wherein: the oxidation treatment adopts one or more of chemical oxidation, electrochemical oxidation, ultraviolet catalytic oxidation, air oxidation or medicament oxidation; and/or
The clean water obtained in step 4b) is recycled to the wet scrubbing unit (1).
4. The method according to any one of claims 1-3, wherein: the acid flue gas is SRG gas, and the SRG gas is: the multi-pollutant flue gas is adsorbed by an adsorption tower (10), an adsorbent is arranged in the adsorption tower (10), and the adsorbent adsorbed with pollutants is obtained by analyzing through an analyzing tower (11); and/or
The suspended matters are precipitated into carbon powder in the step 2).
5. The method of claim 4, wherein: the adsorbent is solid or liquid; and/or
The carbon powder in the step 2) is used for synthesizing large-particle activated carbon through a carbon powder recycling process and returns to the adsorption tower (10) for recycling.
6. The method of claim 5, wherein: the adsorbent is one or more of activated carbon, molecular sieves, MOFs, ionic liquid and organic amine.
7. The method of claim 6, wherein: the ammonia-containing flue gas obtained in step 4a) is conveyed to an adsorption tower (10) for cyclic treatment.
8. The method of any one of claims 1-3, 5-7, wherein: in the step 1), the solution adopted by the wet washing is an acidic solution.
9. The method of claim 4, wherein: in the step 1), the solution adopted by the wet washing is an acidic solution.
10. The method of claim 8, wherein: the pH value of the acidic solution is 0-7.
11. The method of claim 9, wherein: the pH value of the acidic solution is 0-7.
12. The method according to claim 10 or 11, characterized in that: the pH value of the acidic solution is 1-6.
13. The method of claim 12, wherein: the pH value of the acidic solution is 2-5.
14. The method of claim 13, wherein: the acid solution is dilute sulfuric acid or dilute hydrochloric acid; in the wet washing process, the volume flow ratio of the SRG gas to the acidic solution is 1: 10-100.
15. The method of claim 14, wherein: in the wet washing process, the volume flow ratio of the SRG gas to the acidic solution is 1: 20-80.
16. The method of claim 15, wherein: in the wet washing process, the volume flow ratio of the SRG gas to the acidic solution is 1: 30-60.
17. The method of any one of claims 1-3, 5-7, 9-11, 13-16, wherein: the acidic flue gas washing wastewater comprises one or more of suspended matters, metal ions, ammonia nitrogen, fluorine and chlorine and organic pollutants.
18. The method of claim 4, wherein: the acidic flue gas washing wastewater comprises one or more of suspended matters, metal ions, ammonia nitrogen, fluorine and chlorine and organic pollutants.
19. The method of claim 17, wherein: the concentration of suspended matters in the clear liquid after acidic filtration is 1-80 mg/L; and/or
The metal ions are one or more of iron, copper, lead, calcium, zinc, cadmium, cobalt, nickel and aluminum.
20. The method of claim 18, wherein: the concentration of suspended matters in the clear liquid after acidic filtration is 1-80 mg/L; and/or
The metal ions are one or more of iron, copper, lead, calcium, zinc, cadmium, cobalt, nickel and aluminum.
21. The method according to claim 19 or 20, characterized in that: the concentration of suspended matters in the clear liquid after acidic filtration is 2-50 mg/L.
22. The method of any one of claims 1-3, 5-7, 9-11, 13-16, 18-20, wherein: in step 3), the pH of the clear solution is adjusted to 7.2-9.
23. The method of claim 4, wherein: in step 3), the pH of the clear solution is adjusted to 7.2-9.
24. The method of claim 22, wherein: in step 3), the pH of the clear solution is adjusted to 7.5-8.5.
25. The method of claim 23, wherein: in step 3), the pH of the clear solution is adjusted to 7.5-8.5.
26. The method of any one of claims 1-3, 5-7, 9-11, 13-16, 18-20, 23-25, wherein: in the step 4a), the atomization specifically comprises: dispersing the mixture of the clear liquid and the alkali liquor into small fog drops with the particle size of 10-100 mu m by using an atomizer; and/or
The dust removal treatment in the step 4a) adopts dry dust removal; after the dust removal treatment, the crystallized salt is discharged from a solid outlet of the dust remover (5).
27. The method of claim 4, wherein: in the step 4a), the atomization specifically comprises: dispersing the mixture of the clear liquid and the alkali liquor into small fog drops with the particle size of 10-100 mu m by using an atomizer; and/or
The dust removal treatment in the step 4a) adopts dry dust removal; after the dust removal treatment, the crystallized salt is discharged from a solid outlet of the dust remover (5).
28. The method of claim 26, wherein: the particle size of the small fog drops is 15-80 mu m; and/or
The dust removal treatment adopts electric dust removal, cloth bag dust removal or ceramic dust removal.
29. The method of claim 27, wherein: the particle size of the small fog drops is 15-80 mu m; and/or
The dust removal treatment adopts electric dust removal, cloth bag dust removal or ceramic dust removal.
30. The method of claim 28 or 29, wherein: the particle size of the small fog drops is 20-50 mu m; and/or
The dust removal treatment adopts cloth bag dust removal.
31. The method of claim 30, wherein: the alkali liquor is one or more of soluble hydroxide, soluble carbonate and soluble bicarbonate.
32. The method of claim 31, wherein: the alkali liquor is sodium hydroxide.
33. The method of claim 32, wherein: the addition amount of the alkali liquor is 0-0.5 times of the amount of the clear liquor.
34. The method of claim 33, wherein: the addition amount of the alkali liquor is 0.01-0.25 time of the amount of the clear liquor.
35. The method of claim 34, wherein: the addition amount of the alkali liquor is 0.05-0.1 time of the amount of the clear liquor.
36. The method of claim 26, wherein: in the step 4b), the ammonia removal treatment specifically comprises: adding strong base into the salt-containing wastewater obtained in the step 3); adjusting the pH value of the salt-containing wastewater to 10-14, and separating and recovering ammonia to obtain an ammonia-containing byproduct and ammonia-removing wastewater; and/or
In the step 4b), the cooling and condensing treatment specifically comprises the following steps: and adjusting the temperature of the ammonia removal wastewater to low temperature, and condensing and crystallizing the salt in the ammonia removal wastewater to obtain crystallized salt and clean water.
37. The method of claim 36, wherein: adjusting the pH value of the salt-containing wastewater to 10.5-13.5; and/or
The low temperature is 0-30 ℃.
38. The method of claim 37, wherein: adjusting the pH value of the salt-containing wastewater to 11-13; and/or
The low temperature is 5-25 ℃.
39. The method of claim 38, wherein: the separation adopts one or more methods of blowing to remove ammonia, membrane separation and evaporation to remove ammonia; and/or
The low temperature is 10-20 ℃.
40. The method of claim 39, wherein: the strong base is one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide; and/or
The crystallization salt is one or more of sulfate, chloride and fluoride.
41. The method of claim 4, wherein: the multi-pollutant flue gas is SO2Mixed flue gas consisting of one or more of NOx, dust, VOCs and heavy metals; and/or
The multi-pollutant flue gas is derived from complex gas containing sulfur dioxide generated in steel, electric power, colored, petrochemical, chemical industry or building material industry.
42. The method of any one of claims 5-7, 9, 11, 18, 20, 23, 25, 27, 29, wherein: the multi-pollutant flue gas is SO2Mixed flue gas consisting of one or more of NOx, dust, VOCs and heavy metals; and/or
The multi-pollutant flue gas is derived from complex gas containing sulfur dioxide generated in steel, electric power, colored, petrochemical, chemical industry or building material industry.
43. The method of claim 41, wherein: the volume content of sulfur dioxide in the multi-pollutant flue gas is 0.01-1%; the temperature of the multi-pollutant flue gas is 100-200 ℃.
44. The method of claim 42, wherein: the volume content of sulfur dioxide in the multi-pollutant flue gas is 0.01-1%; the temperature of the multi-pollutant flue gas is 100-200 ℃.
45. The method of claim 43 or 44, wherein: the volume content of sulfur dioxide in the multi-pollutant flue gas is 0.03-0.8%; the temperature of the multi-pollutant flue gas is 120-180 ℃.
46. The method of claim 45, wherein: the volume content of sulfur dioxide in the multi-pollutant flue gas is 0.05-0.5%; the temperature of the multi-pollutant flue gas is 130-160 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810106012.0A CN110127918B (en) | 2018-02-02 | 2018-02-02 | Zero-discharge treatment method and device for acidic flue gas washing wastewater |
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| CN110745989B (en) * | 2019-10-25 | 2022-02-18 | 湖南中冶长天节能环保技术有限公司 | Activated carbon flue gas purification acid-making wastewater zero-discharge process and system |
| CN110921958A (en) * | 2019-12-17 | 2020-03-27 | 武汉钢铁有限公司 | Acid-making wastewater recycling system and method by sintering flue gas activated carbon desulfurization process |
| CN113754160B (en) * | 2020-06-01 | 2023-06-23 | 中冶长天国际工程有限责任公司 | Method and system for cleanly recycling calcium chloride from acidic flue gas washing wastewater |
| CN113754162A (en) * | 2020-06-01 | 2021-12-07 | 中冶长天国际工程有限责任公司 | Method and system for recovering chloride by crystallizing acidic washing wastewater |
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| CN111960592A (en) * | 2020-08-04 | 2020-11-20 | 中冶北方（大连）工程技术有限公司 | Treatment system and treatment method for activated carbon desulfurization and denitrification acid-making wastewater |
| CN114053840B (en) * | 2020-08-05 | 2023-06-23 | 中冶长天国际工程有限责任公司 | Internal circulation cleaning treatment method and system for cyanide-containing SRG gas |
| CN112570023B (en) * | 2020-12-28 | 2022-12-27 | 太原理工大学 | Ionic liquid modified CuY molecular sieve catalyst and preparation method and application thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102503015A (en) * | 2011-11-25 | 2012-06-20 | 武汉兴能环保技术有限公司 | Method for treating wastewater generated by ammonia process desulfurization |
| CN102765829A (en) * | 2011-05-04 | 2012-11-07 | 上海焦化有限公司 | Treatment method for urea-containing high concentration copper ammonium wastewater |
| CN102942280A (en) * | 2012-11-14 | 2013-02-27 | 北京赛科康仑环保科技有限公司 | Method for decomplexing heavy metal ammonia complex in high-concentration ammonia-nitrogen wastewater |
| CN103140274A (en) * | 2011-03-22 | 2013-06-05 | 三菱重工业株式会社 | Air pollution control system and air pollution control method, spray drying device of dewatering filtration fluid from desulfurization discharged water, and method thereof |
| CN103466870A (en) * | 2013-08-22 | 2013-12-25 | 苏州苏净环保工程有限公司 | Material recovery method of wastewater containing high-concentration ammonia-nitrogen and heavy metal ions and treatment system |
| CN203486994U (en) * | 2013-08-22 | 2014-03-19 | 苏州苏净环保工程有限公司 | Treatment system for wastewater containing high-concentration ammonia nitrogen and heavy metal ions |
| CN203529996U (en) * | 2013-09-27 | 2014-04-09 | 中南大学 | Cuprammouium complexing wastewater treatment device |
| WO2014114728A1 (en) * | 2013-01-25 | 2014-07-31 | Cm-Institute (Civilisations Matter) E.V. | Process for operating a water treatment plant, corresponding water treatment plant and use of the process for treating untreated water |
| CN104428257A (en) * | 2012-07-03 | 2015-03-18 | 三菱重工业株式会社 | Wastewater treatment system and combined power generation equipment |
| WO2015084579A1 (en) * | 2013-12-05 | 2015-06-11 | Exxonmobil Research And Engineering Company | Improved corrosion control in acid gas removal equipment by the situ generation of polysulfide ions |
-
2018
- 2018-02-02 CN CN201810106012.0A patent/CN110127918B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103140274A (en) * | 2011-03-22 | 2013-06-05 | 三菱重工业株式会社 | Air pollution control system and air pollution control method, spray drying device of dewatering filtration fluid from desulfurization discharged water, and method thereof |
| CN102765829A (en) * | 2011-05-04 | 2012-11-07 | 上海焦化有限公司 | Treatment method for urea-containing high concentration copper ammonium wastewater |
| CN102503015A (en) * | 2011-11-25 | 2012-06-20 | 武汉兴能环保技术有限公司 | Method for treating wastewater generated by ammonia process desulfurization |
| CN104428257A (en) * | 2012-07-03 | 2015-03-18 | 三菱重工业株式会社 | Wastewater treatment system and combined power generation equipment |
| CN102942280A (en) * | 2012-11-14 | 2013-02-27 | 北京赛科康仑环保科技有限公司 | Method for decomplexing heavy metal ammonia complex in high-concentration ammonia-nitrogen wastewater |
| WO2014114728A1 (en) * | 2013-01-25 | 2014-07-31 | Cm-Institute (Civilisations Matter) E.V. | Process for operating a water treatment plant, corresponding water treatment plant and use of the process for treating untreated water |
| CN103466870A (en) * | 2013-08-22 | 2013-12-25 | 苏州苏净环保工程有限公司 | Material recovery method of wastewater containing high-concentration ammonia-nitrogen and heavy metal ions and treatment system |
| CN203486994U (en) * | 2013-08-22 | 2014-03-19 | 苏州苏净环保工程有限公司 | Treatment system for wastewater containing high-concentration ammonia nitrogen and heavy metal ions |
| CN203529996U (en) * | 2013-09-27 | 2014-04-09 | 中南大学 | Cuprammouium complexing wastewater treatment device |
| WO2015084579A1 (en) * | 2013-12-05 | 2015-06-11 | Exxonmobil Research And Engineering Company | Improved corrosion control in acid gas removal equipment by the situ generation of polysulfide ions |
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