CN115108689A - Method for purifying nickel plating wastewater - Google Patents
Method for purifying nickel plating wastewater Download PDFInfo
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- CN115108689A CN115108689A CN202210924633.6A CN202210924633A CN115108689A CN 115108689 A CN115108689 A CN 115108689A CN 202210924633 A CN202210924633 A CN 202210924633A CN 115108689 A CN115108689 A CN 115108689A
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- nickel plating
- coagulation
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- plating wastewater
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 325
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 160
- 238000007747 plating Methods 0.000 title claims abstract description 150
- 239000002351 wastewater Substances 0.000 title claims abstract description 147
- 238000000034 method Methods 0.000 title claims abstract description 42
- 238000011282 treatment Methods 0.000 claims abstract description 132
- 238000005345 coagulation Methods 0.000 claims abstract description 111
- 230000015271 coagulation Effects 0.000 claims abstract description 111
- 239000007788 liquid Substances 0.000 claims abstract description 87
- 238000005189 flocculation Methods 0.000 claims abstract description 73
- 230000016615 flocculation Effects 0.000 claims abstract description 73
- 238000000926 separation method Methods 0.000 claims abstract description 62
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 36
- 238000010979 pH adjustment Methods 0.000 claims abstract description 34
- 239000007800 oxidant agent Substances 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 230000001590 oxidative effect Effects 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000005728 strengthening Methods 0.000 claims abstract description 21
- 239000007791 liquid phase Substances 0.000 claims abstract description 19
- 238000000746 purification Methods 0.000 claims abstract description 19
- 238000011221 initial treatment Methods 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims description 173
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 59
- 239000000701 coagulant Substances 0.000 claims description 58
- 239000012266 salt solution Substances 0.000 claims description 27
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 22
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 18
- 239000008103 glucose Substances 0.000 claims description 18
- 239000008394 flocculating agent Substances 0.000 claims description 16
- 230000020477 pH reduction Effects 0.000 claims description 14
- 239000003638 chemical reducing agent Substances 0.000 claims description 13
- 230000007062 hydrolysis Effects 0.000 claims description 11
- 238000006460 hydrolysis reaction Methods 0.000 claims description 11
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 10
- 239000000460 chlorine Substances 0.000 claims description 10
- 229910052801 chlorine Inorganic materials 0.000 claims description 10
- 238000006396 nitration reaction Methods 0.000 claims description 5
- 229910000859 α-Fe Inorganic materials 0.000 claims description 4
- 230000003301 hydrolyzing effect Effects 0.000 claims description 3
- 238000005202 decontamination Methods 0.000 claims 2
- 230000035484 reaction time Effects 0.000 claims 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 10
- 239000011574 phosphorus Substances 0.000 abstract description 10
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 10
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003344 environmental pollutant Substances 0.000 abstract description 2
- 231100000719 pollutant Toxicity 0.000 abstract description 2
- 239000004912 1,5-cyclooctadiene Substances 0.000 abstract 1
- 238000007792 addition Methods 0.000 description 76
- 238000006722 reduction reaction Methods 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 238000004062 sedimentation Methods 0.000 description 12
- 239000000126 substance Substances 0.000 description 10
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 9
- 239000000292 calcium oxide Substances 0.000 description 9
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 9
- 238000000909 electrodialysis Methods 0.000 description 7
- 238000004065 wastewater treatment Methods 0.000 description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000011790 ferrous sulphate Substances 0.000 description 6
- 235000003891 ferrous sulphate Nutrition 0.000 description 6
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 229910052979 sodium sulfide Inorganic materials 0.000 description 6
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 6
- 229910001385 heavy metal Inorganic materials 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229910001453 nickel ion Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 235000015165 citric acid Nutrition 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229960002089 ferrous chloride Drugs 0.000 description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 238000004886 process control Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- -1 suspended matters Chemical compound 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 206010027439 Metal poisoning Diseases 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 241000122973 Stenotrophomonas maltophilia Species 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- TVJORGWKNPGCDW-UHFFFAOYSA-N aminoboron Chemical compound N[B] TVJORGWKNPGCDW-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 208000010501 heavy metal poisoning Diseases 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000013048 microbiological method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 1
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- 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
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/30—Aerobic and anaerobic processes
- C02F3/302—Nitrification and denitrification treatment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/30—Aerobic and anaerobic processes
- C02F3/308—Biological phosphorus removal
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemically Coating (AREA)
Abstract
The invention relates to a method for purifying nickel plating wastewater, which comprises the following steps: adding ferrous salt into the nickel plating wastewater for pretreatment, then sequentially carrying out first pH adjustment, first coagulation, first flocculation and solid-liquid separation, adding an oxidant into the obtained liquid phase for strengthening reaction, and then carrying out the steps ofCarrying out reduction, second pH value adjustment, second coagulation, second flocculation and solid-liquid separation for the second time to obtain a primary treatment liquid; subjecting the obtained primary treatment solution to a third pH adjustment, and then sequentially subjecting to A 2 Performing O treatment and AO treatment, and then performing solid-liquid separation to obtain secondary treatment liquid; and (3) carrying out fourth pH value adjustment on the obtained secondary treatment liquid, and then sequentially carrying out Fenton treatment, fifth pH value adjustment, third coagulation, third flocculation and solid-liquid separation to obtain the discharge water. The purification method adopts a specific treatment process to purify pollutants such as Ni, phosphorus, COD, ammonia nitrogen and the like in the nickel plating wastewater, thereby meeting the emission requirement.
Description
Technical Field
The invention relates to the field of sewage treatment, in particular to a method for purifying nickel plating wastewater.
Background
At present, chemical nickel wastewater in industrial wastewater mainly comes from a chemical plating process of a production line, the wastewater contains a nickel plating raw material, a reducing agent and an additive, and mainly comprises nickel sulfamate, hypophosphite and citric acid, and the chemical nickel wastewater is very difficult to treat due to the existence of the substances. The chemical nickel treatment process commonly used at present mainly comprises a chemical precipitation method, a Fenton oxidation method and an electrocatalytic oxidation method, and the advanced treatment process comprises a phosphorus removal agent, special resin, membrane treatment, evaporative crystallization and the like.
For example, CN109553224A discloses a chemical nickel plating wastewater treatment device and a method thereof. The chemical nickel plating wastewater treatment equipment sequentially comprises a pretreatment device, an electrodialysis device, a tubular microporous filtering device and a metal recovery device. The apparatus combines homogeneous membrane electrodialysis with electrocatalytic oxidation techniques. In the electrodialysis process, anions and cations in the solution are enriched in the electrodialysis concentration chamber, and nickel ions as cations are continuously enriched in the electrodialysis concentration water chamber and are close to the anion membrane. And compounding a nickel reduction catalyst on one side of the cathode membrane facing the concentrated water chamber to enable nickel ions to perform cathode reduction reaction to generate nickel powder, and enabling the nickel powder to flow out of the electrodialyzer through electrodialysis circulation, wherein fresh water of the electrodialysis is recycled, and the metal nickel powder is recycled by the microporous filter. The nickel recovery device has the advantages of simple structure, capability of effectively saving used medicament, energy conservation, environmental protection, high nickel recovery rate and material saving.
CN102616940A discloses a purification treatment method of nickel plating waste water, which adopts a microbiological method, firstly simulates and prepares nickel plating water, cultures stenotrophomonas maltophilia as a microbial strain, enriches and purifies, then mixes the strain with the nickel plating waste water, and carries out oscillation purification treatment on heavy metal in the nickel plating waste water, the treatment purification rate is 98.5 percent, reaches the reclaimed water standard specified by the national standard, can be used for washing and irrigating farmlands, and has advanced, rapid and short process flow, real and accurate data, no environmental pollution, high purification rate of the nickel plating water, industrial treatment, ideal purification treatment method of the nickel plating waste water, and can also be used for treating and purifying other waste water containing heavy metal.
However, in order to discharge the nickel-containing wastewater by reaching the standard at a single port, most enterprises add phosphorus removal agents, special resins, membrane treatment, evaporators and other processes for further advanced treatment after flocculation treatment, so that the investment and operating cost of wastewater treatment facilities are increased, and the risk of overproof and production halt of the enterprises is increased due to the instability of equipment operation, so that the problems of low standard reaching rate, poor operating stability, high operating cost, high equipment investment and incapability of directly reaching the standard and discharging system effluent are caused.
Disclosure of Invention
In view of the problems in the prior art, one of the purposes of the invention is to provide a method for purifying nickel plating wastewater, which solves the problems of low standard reaching rate, poor operation stability, high operation cost, high equipment investment and incapability of directly reaching the standard and discharging system effluent in the conventional nickel plating wastewater treatment process.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a purification method of nickel plating wastewater, which comprises the following steps:
(1) adding ferrous salt into the nickel plating wastewater for pretreatment, then sequentially carrying out first pH adjustment, first coagulation, first flocculation and first solid-liquid separation, adding an oxidant into the obtained liquid phase for strengthening reaction, and then sequentially carrying out reduction, second pH adjustment, second coagulation, second flocculation and second solid-liquid separation to obtain a primary treatment solution;
(2) the primary treatment liquid obtained in the step (1) is subjected to third pH value adjustment, and then A is sequentially carried out 2 Performing O treatment and AO treatment, and then performing third solid-liquid separation to obtain secondary treatment liquid;
(3) and (3) performing fourth pH value adjustment on the secondary treatment liquid obtained in the step (2), and then sequentially performing Fenton treatment, fifth pH value adjustment, third coagulation, third flocculation and fourth solid-liquid separation to obtain discharge water.
The purification method provided by the invention adopts a specific purification process, and firstly reasonably removes heavy metal ions, hypophosphorous acid and a part of total nitrogen so as to ensure that the removal rate of the total phosphorus and the total nitrogen of the system is improved; then removing COD, total nitrogen, ammonia nitrogen and a small part of total phosphorus through a biochemical treatment process, further carrying out deep oxidation reaction on nickel and total phosphorus in the wastewater in combination with final treatment, and enabling biochemical indexes such as COD, total nitrogen and the like to meet the discharge requirement so as to meet the final discharge requirement. Wherein, the pretreatment function is as follows: most of simple pollution factors such as heavy metal copper, nickel ions, suspended matters, orthophosphoric acid and the like in a molecular state are removed, the dosage of a subsequent strengthening reaction medicament is reduced, and good water quality conditions are provided for the subsequent strengthening reaction. The effect of enhancing the reaction: most of ammonia nitrogen in the wastewater is removed, and the hypophosphorous acid and chemical nickel in the wastewater are oxidized, so that the treatment effect is further improved, the heavy metal content is reduced, good water quality conditions are provided for subsequent biochemistry, and the risk of heavy metal poisoning of a biochemical system is reduced. A. the 2 And (4) O treatment: degrading COD, performing denitrification and dephosphorization reaction by using activated sludge, and reducing inorganic indexes such as ammonia nitrogen, total phosphorus, COD and the like. AO treatment: the denitrification and dephosphorization effect is enhanced, the highest denitrification effect of the primary biochemical system can only reach 70-80 percent, and the effluent can not reach the standard. And (3) Fenton treatment: as an advanced treatment of effluentThe system further oxidizes the phosphorus and the chemical nickel, and each pollution factor reaches the emission standard after Fenton treatment.
In the invention, the nickel plating wastewater mainly comes from a workshop chemical nickel plating process, wherein the main raw materials in the process are nickel sulfamate, nickel sulfate hexahydrate, a nickel brightener and the like, and the nickel plating wastewater also contains a large amount of reducing agents such as hypophosphite, hydrazine, borohydride, amino borane, additives such as citric acid, tartaric acid, malic acid, ammonium chloride and the like.
In a preferred embodiment of the present invention, the ferrous salt solution in the step (1) may have a mass concentration of 10 to 12%, for example, 10%, 10.2%, 10.4%, 10.6%, 10.8%, 11%, 11.2%, 11.4%, 11.6%, 11.8%, or 12%, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
Preferably, the ferrous salt solution added in step (1) is 8-9% of the volume of the nickel plating wastewater, for example, 8%, 8.1%, 8.2%, 8.3%, 8.4%, 8.5%, 8.6%, 8.7%, 8.8%, 8.9% or 9% may be used, but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the pretreatment time in step (1) is 40-50min, for example, 40min, 40.2min, 40.4min, 40.6min, 40.8min, 41min, 41.2min, 41.4min, 41.6min, 41.8min, 42min, 42.2min, 42.4min, 42.6min, 42.8min, 43min, 43.2min, 43.4min, 43.6min, 43.8min, 44min, 44.2min, 44.4min, 44.6min, 44.8min, 45min, 45.2min, 45.4min, 45.6min, 45.8min, 46min, 46.2min, 46.4min, 46.6min, 46.8min, 47min, 47.2min, 47.4min, 47.6min, 47.8min, 48min, 48.2min, 48.4min, 48.6min, 49.8min, 49.49 min, or the like, and the same values as those listed above are not limited to the other values.
Preferably, the end point pH of said first pH adjustment in step (1) is between 11 and 11.5, which may be, for example, 11, 11.1, 11.2, 11.3, 11.4 or 11.5, but is not limited to the values recited, and other values not recited in this range are equally applicable.
Preferably, the first coagulation is performed by keeping for 15-20min after the first pH adjustment in step (1) reaches the end point pH, for example, 15min, 15.2min, 15.4min, 15.6min, 15.8min, 16min, 16.2min, 16.4min, 16.6min, 16.8min, 17min, 17.2min, 17.4min, 17.6min, 17.8min, 18min, 18.2min, 18.4min, 18.6min, 18.8min, 19min, 19.2min, 19.4min, 19.6min, 19.8min or 20min, etc., but not limited to the values listed, and the other values not listed in this range are also applicable.
As a preferable embodiment of the present invention, a sulfide solution and a coagulant solution are added to the first coagulation in the step (1).
Preferably, the addition amount of the sulfide solution in the first coagulation in the step (1) is 2 to 3% of the volume of the nickel plating wastewater, for example, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, or 3% may be used, but is not limited to the enumerated values, and other unrecited values in the range are also applicable.
Preferably, the sulfide solution used in the first coagulation in the step (1) has a mass concentration of 5 to 6%, for example, 5%, 5.1%, 5.2%, 5.3%, 5.4%, 5.5%, 5.6%, 5.7%, 5.8%, 5.9%, or 6%, and the like, but is not limited to the values listed, and other values not listed in this range are also applicable.
Preferably, the addition amount of the coagulant solution in the first coagulation in the step (1) is 2 to 3% by volume of the nickel plating wastewater, for example, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, or 3% by volume, but not limited to the enumerated values, and other unrecited values in the range are also applicable.
Preferably, the mass concentration of the coagulant solution used in the first coagulation in step (1) is 5 to 6%, and may be, for example, 5%, 5.1%, 5.2%, 5.3%, 5.4%, 5.5%, 5.6%, 5.7%, 5.8%, 5.9%, or 6%, etc., but is not limited to the values listed, and other values not listed in this range are also applicable.
Preferably, the time of the first coagulation in step (1) is 20-30min, such as 20min, 20.5min, 21min, 21.5min, 22min, 22.5min, 23min, 23.5min, 24min, 24.5min, 25min, 25.5min, 26min, 26.5min, 27min, 27.5min, 28min, 28.5min, 29min, 29.5min or 30min, etc., but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the addition amount of the flocculant solution in the first flocculation in the step (1) is 5 to 6 per thousand of the volume of the nickel plating wastewater, for example, 5 per thousand, 5.1 per thousand, 5.2 per thousand, 5.3 per thousand, 5.4 per thousand, 5.5 per thousand, 5.6 per thousand, 5.7 per thousand, 5.8 per thousand, 5.9 per thousand or 6 per thousand, etc., but is not limited to the enumerated values, and other unrecited values in the range are also applicable.
Preferably, the concentration of the flocculant solution used in the first flocculation in step (1) is 0.2 to 0.3%, and may be, for example, 0.2%, 0.21%, 0.22%, 0.23%, 0.24%, 0.25%, 0.26%, 0.27%, 0.28%, 0.29%, or 0.3%, etc., but is not limited to the recited values, and other values not recited in this range are also applicable.
Preferably, the time of the first flocculation in step (1) is 20-30min, such as 20min, 20.5min, 21min, 21.5min, 22min, 22.5min, 23min, 23.5min, 24min, 24.5min, 25min, 25.5min, 26min, 26.5min, 27min, 27.5min, 28min, 28.5min, 29min, 29.5min or 30min, etc., but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the surface load is controlled to be less than 1.5m in the first solid-liquid separation in the step (1) 3 /(m 2 H) may be, for example, 1.4m 3 /(m 2 ·h)、1.3m 3 /(m 2 ·h)、1.2m 3 /(m 2 ·h)、1.1m 3 /(m 2 ·h)、1.0m 3 /(m 2 ·h)、0.9m 3 /(m 2 ·h)、0.8m 3 /(m 2 ·h)、0.7m 3 /(m 2 ·h)、0.6m 3 /(m 2 ·h)、0.5m 3 /(m 2 ·h)、0.4m 3 /(m 2 ·h)、0.3m 3 /(m 2 H) or 0.2m 3 /(m 2 H) and the like, but are not limited to the numerical values listed, the rangeOther values not listed within the enclosure are equally applicable.
As a preferable technical scheme of the invention, the oxidant in the step (1) comprises a chlorine-containing oxidant solution.
Preferably, the amount of the oxidizing agent added in step (1) is 10 to 12% by volume of the nickel plating wastewater, for example, 11% o, 11.2% o, 11.4% o, 11.6% o, 11.8% o, 12% o, 12.2% o, 12.4% o, 12.6% o, 12.8% o or 13% by volume, but not limited to the enumerated values, and other unrecited values in the range are also applicable.
Preferably, the mass concentration of the oxidizing agent in step (1) is 10 to 12%, and may be, for example, 10%, 10.2%, 10.4%, 10.6%, 10.8%, 11%, 11.2%, 11.4%, 11.6%, 11.8%, 10%, or the like, but is not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the strengthening reaction in step (1) is carried out for 4-8h, such as 4h, 4.2h, 4.4h, 4.6h, 4.8h, 5h, 5.2h, 5.4h, 5.6h, 5.8h, 6h, 6.2h, 6.4h, 6.6h, 6.8h, 7h, 7.2h, 7.4h, 7.6h, 7.8h or 8h, etc., but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the addition amount of the reducing agent in the reduction in the step (1) is 8 to 9% of the volume of the nickel plating wastewater, for example, 8%, 8.1%, 8.2%, 8.3%, 8.4%, 8.5%, 8.6%, 8.7%, 8.8%, 8.9%, or 8% may be used, but not limited to the enumerated values, and other values not enumerated in the range are also applicable.
Preferably, the mass concentration of the reducing agent used in the reduction in the step (1) is 10 to 12%, for example, 10%, 10.2%, 10.4%, 10.6%, 10.8%, 11%, 11.2%, 11.4%, 11.6%, 11.8%, or 12%, etc., but not limited to the values listed, and other values not listed in this range are also applicable.
Preferably, the reduction time in step (1) is 30-40min, such as 30min, 30.5min, 31min, 31.5min, 32min, 32.5min, 33min, 33.5min, 34min, 34.5min, 35min, 35.5min, 36min, 36.5min, 37min, 37.5min, 38min, 38.5min, 39min, 39.5min or 40min, but not limited to the recited values, and other values not recited in this range are also applicable.
Preferably, the final pH of the second pH adjustment in step (1) is 11-11.5, such as 11, 11.1, 11.2, 11.3, 11.4 or 11.5, but not limited to the recited values, and other values not recited in this range are equally applicable.
Preferably, the second coagulation is performed for 15-20min after the second pH adjustment in step (1) reaches the end point pH, for example, 15min, 15.2min, 15.4min, 15.6min, 15.8min, 16min, 16.2min, 16.4min, 16.6min, 16.8min, 17min, 17.2min, 17.4min, 17.6min, 17.8min, 18min, 18.2min, 18.4min, 18.6min, 18.8min, 19min, 19.2min, 19.4min, 19.6min, 19.8min, or 20min, etc., but not limited to the recited values, and other values in the range are also applicable.
As a preferable embodiment of the present invention, a sulfide solution and a coagulant solution are added to the second coagulation in the step (1).
Preferably, the sulfide solution used in the second coagulation in the step (1) has a mass concentration of 5 to 6%, for example, 5%, 5.1%, 5.2%, 5.3%, 5.4%, 5.5%, 5.6%, 5.7%, 5.8%, 5.9%, or 6%, and the like, but is not limited to the values listed, and other values not listed in this range are also applicable.
Preferably, the addition amount of the sulfide solution in the second coagulation in the step (1) is 3 to 4% by volume of the nickel plating wastewater, for example, 3%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, or 4% by volume, but not limited to the enumerated values, and other values not enumerated in this range are also applicable.
Preferably, the mass concentration of the coagulant solution used in the second coagulation in step (1) is 5 to 6%, and may be, for example, 5%, 5.1%, 5.2%, 5.3%, 5.4%, 5.5%, 5.6%, 5.7%, 5.8%, 5.9%, or 6%, etc., but is not limited to the values listed, and other values not listed in this range are also applicable.
Preferably, the addition amount of the coagulant solution in the second coagulation in the step (1) is 3 to 4% by volume of the nickel plating wastewater, for example, 3%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, or 4% by volume, but not limited to the enumerated values, and other values not enumerated in this range are also applicable.
Preferably, the time of the second coagulation in step (1) is 20-30min, such as 20min, 20.5min, 21min, 21.5min, 22min, 22.5min, 23min, 23.5min, 24min, 24.5min, 25min, 25.5min, 26min, 26.5min, 27min, 27.5min, 28min, 28.5min, 29min, 29.5min or 30min, etc., but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the mass concentration of the flocculant used in the second flocculation in step (1) is 0.2 to 0.3%, and for example, it may be 0.2%, 0.21%, 0.22%, 0.23%, 0.24%, 0.25%, 0.26%, 0.27%, 0.28%, 0.29%, or 0.3%, etc., but is not limited to the enumerated values, and other values not enumerated within this range are also applicable.
Preferably, the amount of the flocculant used in the second flocculation in step (1) is 5 to 6% by volume of the nickel plating wastewater, for example, 5%, 5.1%, 5.2%, 5.3%, 5.4%, 5.5%, 5.6%, 5.7%, 5.8%, 5.9%, or 6% by volume, but not limited to the enumerated values, and other unrecited values in the range are also applicable.
Preferably, the time of the second flocculation in step (1) is 20-30min, such as 20min, 20.5min, 21min, 21.5min, 22min, 22.5min, 23min, 23.5min, 24min, 24.5min, 25min, 25.5min, 26min, 26.5min, 27min, 27.5min, 28min, 28.5min, 29min, 29.5min or 30min, etc., but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the surface load is controlled to be less than 1m in the second solid-liquid separation in the step (1) 3 /(m 2 H) may be, for example, 0.95m 3 /(m 2 ·h)、0.9m 3 /(m 2 ·h)、0.8m 3 /(m 2 ·h)、0.7m 3 /(m 2 ·h)、0.6m 3 /(m 2 ·h)、0.5m 3 /(m 2 ·h)、0.4m 3 /(m 2 ·h)、0.3m 3 /(m 2 H) or 0.2m 3 /(m 2 H) and the like, but are not limited to the values recited, and other values not recited within the range are equally applicable.
In a preferred embodiment of the present invention, the final pH of the third pH adjustment in step (2) is 8.8 to 9.3, for example, 8.8, 8.9, 9, 9.1, 9.2 or 9.3, but is not limited to the above-mentioned values, and other values not listed in this range are also applicable.
Preferably, the third pH value adjustment in the step (2) is carried out for 30-40min after reaching the end point pH value 2 The O treatment may be, for example, 30min, 30.5min, 31min, 31.5min, 32min, 32.5min, 33min, 33.5min, 34min, 34.5min, 35min, 35.5min, 36min, 36.5min, 37min, 37.5min, 38min, 38.5min, 39min, 39.5min or 40min, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
As a preferable embodiment of the present invention, A in the step (2) 2 The O treatment comprises hydrolytic acidification, primary denitrification and primary nitrification which are sequentially carried out.
Preferably, the hydrolytic acidification in step (2) is carried out for 15-20h, such as 15h, 15.2h, 15.4h, 15.6h, 15.8h, 16h, 16.2h, 16.4h, 16.6h, 16.8h, 17h, 17.2h, 17.4h, 17.6h, 17.8h, 18h, 18.2h, 18.4h, 18.6h, 18.8h, 19h, 19.2h, 19.4h, 19.6h, 19.8h or 20h, etc., but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the addition amount of the glucose solution with the mass concentration of 5-6% used in the primary denitrification in the step (2) is 1-2 per mill of the volume of the nickel plating wastewater.
In the present invention, the glucose solution used in the primary denitrification may have a mass concentration of 5 to 6%, for example, 5%, 5.1%, 5.2%, 5.3%, 5.4%, 5.5%, 5.6%, 5.7%, 5.8%, 5.9%, or 6%, but is not limited to the values listed, and other values not listed in the range are also applicable.
In the present invention, the amount of the 5 to 6% by mass glucose solution added in the primary denitrification is 1 to 2% by volume of the nickel plating wastewater, and may be, for example, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, or 2%, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
Preferably, the time for the primary denitrification in step (2) is 5-8h, such as 5h, 5.2h, 5.4h, 5.6h, 5.8h, 6h, 6.2h, 6.4h, 6.6h, 6.8h, 7h, 7.2h, 7.4h, 7.6h, 7.8h or 8h, etc., but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the time for the primary nitration in the step (2) is 8 to 12 hours, such as 8 hours, 8.2 hours, 8.4 hours, 8.6 hours, 8.8 hours, 9 hours, 9.2 hours, 9.4 hours, 9.6 hours, 9.8 hours, 10 hours, 10.2 hours, 10.4 hours, 10.6 hours, 10.8 hours, 11 hours, 11.2 hours, 11.4 hours, 11.6 hours, 11.8 hours or 12 hours, etc., but not limited to the enumerated values, and other unrecited values in the range are also applicable.
Preferably, the AO treatment of step (2) includes a secondary denitrification and a secondary nitrification performed in sequence.
Preferably, the time of the secondary denitrification is 3 to 5 hours, for example, 3 hours, 3.1 hours, 3.2 hours, 3.3 hours, 3.4 hours, 3.5 hours, 3.6 hours, 3.7 hours, 3.8 hours, 3.9 hours, 4 hours, 4.1 hours, 4.2 hours, 4.3 hours, 4.4 hours, 4.5 hours, 4.6 hours, 4.7 hours, 4.8 hours, 4.9 hours or 5 hours, etc., but not limited to the enumerated values, and other values not enumerated within the range are also applicable.
Preferably, the addition amount of the glucose solution with the mass concentration of 5-6% used in the secondary denitrification is 3-4 per mill of the volume of the nickel plating wastewater;
in the present invention, the glucose solution used in the secondary denitrification may have a mass concentration of 5 to 6%, for example, 5%, 5.1%, 5.2%, 5.3%, 5.4%, 5.5%, 5.6%, 5.7%, 5.8%, 5.9%, or 6%, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
In the present invention, the amount of the 5 to 6% by mass glucose solution added in the secondary denitrification is 3 to 4% by volume of the nickel plating wastewater, and may be, for example, 3%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, or 4% by volume, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
Preferably, the time of the secondary nitration is 6 to 8 hours, and may be, for example, 6 hours, 6.1 hours, 6.2 hours, 6.3 hours, 6.4 hours, 6.5 hours, 6.6 hours, 6.7 hours, 6.8 hours, 6.9 hours, 7 hours, 7.1 hours, 7.2 hours, 7.3 hours, 7.4 hours, 7.5 hours, 7.6 hours, 7.7 hours, 7.8 hours, 7.9 hours or 8 hours, etc., but is not limited to the enumerated values, and other unrecited values in this range are also applicable.
Preferably, the surface load is controlled to be less than 1m in the third solid-liquid separation in the step (2) 3 /(m 2 H) may be, for example, 0.95m 3 /(m 2 ·h)、0.9m 3 /(m 2 ·h)、0.8m 3 /(m 2 ·h)、0.7m 3 /(m 2 ·h)、0.6m 3 /(m 2 ·h)、0.5m 3 /(m 2 ·h)、0.4m 3 /(m 2 ·h)、0.3m 3 /(m 2 H) or 0.2m 3 /(m 2 H) and the like, but are not limited to the values listed, and other values not listed in the range are equally applicable.
In a preferred embodiment of the present invention, the final pH of the fourth pH adjustment in step (3) is 3.3 to 3.8, for example, 3.3, 3.4, 3.5, 3.6, 3.7 or 3.8, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
Preferably, the fenton treatment is performed for 15-20min after the fourth pH adjustment in step (3) reaches the end point pH, for example, 15min, 15.2min, 15.4min, 15.6min, 15.8min, 16min, 16.2min, 16.4min, 16.6min, 16.8min, 17min, 17.2min, 17.4min, 17.6min, 17.8min, 18min, 18.2min, 18.4min, 18.6min, 18.8min, 19min, 19.2min, 19.4min, 19.6min, 19.8min or 20min, etc., but not limited to the values listed, and other values not listed in this range are also applicable.
Preferably, a ferrous salt solution and a hydrogen peroxide solution are added in the fenton treatment in the step (3).
Preferably, the ferrous salt solution has a mass concentration of 10-12%, for example, 10%, 10.2%, 10.4%, 10.6%, 10.8%, 11%, 11.2%, 11.4%, 11.6%, 11.8%, or 12%, etc., but not limited to the recited values, and other values not recited in this range are also applicable.
Preferably, the hydrogen peroxide solution has a mass concentration of 28 to 30%, for example, 28%, 28.2%, 28.4%, 28.6%, 28.8%, 29%, 29.2%, 29.4%, 29.6%, 29.8%, or 30%, etc., but not limited to the values listed, and other values not listed in this range are also applicable.
Preferably, the addition amount of the ferrite solution used in the fenton treatment in step (3) is 6 to 7% by volume of the nickel plating wastewater, for example, 6%, 6.1%, 6.2%, 6.3%, 6.4%, 6.5%, 6.6%, 6.7%, 6.8%, 6.9% or 7% by volume, but not limited to the enumerated values, and other values not enumerated in this range are also applicable.
Preferably, the amount of the hydrogen peroxide used in the fenton treatment in the step (3) is 1 to 2% by volume of the nickel plating wastewater, and may be, for example, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, or 2% by volume, but is not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the fenton treatment in step (3) is performed for 2 to 6 hours, such as 2 hours, 2.2 hours, 2.4 hours, 2.6 hours, 2.8 hours, 3 hours, 3.2 hours, 3.4 hours, 3.6 hours, 3.8 hours, 4 hours, 4.2 hours, 4.4 hours, 4.6 hours, 4.8 hours, 5 hours, 5.2 hours, 5.4 hours, 5.6 hours, 5.8 hours or 6 hours, but not limited to the enumerated values, and other values not enumerated in this range are also applicable.
Preferably, the final pH of said fifth pH adjustment in step (3) is 11-11.5, such as 11, 11.1, 11.2, 11.3, 11.4 or 11.5, but not limited to the values recited, and other values not recited in this range are equally applicable.
Preferably, the fifth pH adjustment in step (3) is performed for 15-20min after reaching the end point pH, and the third coagulation is performed, for example, 15min, 15.2min, 15.4min, 15.6min, 15.8min, 16min, 16.2min, 16.4min, 16.6min, 16.8min, 17min, 17.2min, 17.4min, 17.6min, 17.8min, 18min, 18.2min, 18.4min, 18.6min, 18.8min, 19min, 19.2min, 19.4min, 19.6min, 19.8min, or 20min, etc., but not limited to the recited values, and other values not recited in the range are also applicable.
As a preferable embodiment of the present invention, a sulfide solution and a coagulant solution are added to the third coagulation in the step (3).
Preferably, the sulfide solution used in the third coagulation in the step (3) has a mass concentration of 5 to 6%, for example, 5%, 5.1%, 5.2%, 5.3%, 5.4%, 5.5%, 5.6%, 5.7%, 5.8%, 5.9%, or 6%, and the like, but is not limited to the values listed, and other values not listed in this range are also applicable.
Preferably, the addition amount of the sulfide solution used in the third coagulation in the step (3) is 1 to 2% by volume of the nickel plating wastewater, and may be, for example, 1% o, 1.1% o, 1.2% o, 1.3% o, 1.4% o, 1.5% o, 1.6% o, 1.7% o, 1.8% o, 1.9% o, or 2% o by volume, but is not limited to the enumerated values, and other unrecited values in this range are also applicable.
Preferably, the mass concentration of the coagulant solution used in the third coagulation in step (3) is 5 to 6%, and may be, for example, 5%, 5.1%, 5.2%, 5.3%, 5.4%, 5.5%, 5.6%, 5.7%, 5.8%, 5.9%, or 6%, but is not limited to the values listed, and other values not listed in this range are also applicable.
Preferably, the addition amount of the coagulant solution used in the third coagulation in the step (3) is 1 to 2% by volume of the nickel plating wastewater, and may be, for example, 1% o, 1.1% o, 1.2% o, 1.3% o, 1.4% o, 1.5% o, 1.6% o, 1.7% o, 1.8% o, 1.9% o or 2% by volume, but is not limited to the enumerated values, and other unrecited values in this range are also applicable.
Preferably, the time of the third coagulation in step (3) is 20-30min, such as 20min, 20.5min, 21min, 21.5min, 22min, 22.5min, 23min, 23.5min, 24min, 24.5min, 25min, 25.5min, 26min, 26.5min, 27min, 27.5min, 28min, 28.5min, 29min, 29.5min or 30min, etc., but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the addition amount of the flocculating agent used in the third flocculation in the step (3) is 6 to 7 per thousand of the volume of the nickel plating wastewater, for example, 6 per thousand, 6.1 per thousand, 6.2 per thousand, 6.3 per thousand, 6.4 per thousand, 6.5 per thousand, 6.6 per thousand, 6.7 per thousand, 6.8 per thousand, 6.9 per thousand or 7 per thousand, and the like, but is not limited to the enumerated values, and other unrecited values in the range are also applicable.
Preferably, the mass concentration of the flocculant used in the third flocculation in step (3) is 0.2 to 0.3%, and for example, it may be 0.2%, 0.21%, 0.22%, 0.23%, 0.24%, 0.25%, 0.26%, 0.27%, 0.28%, 0.29%, or 0.3%, but is not limited to the enumerated values, and other values not enumerated within this range are also applicable.
Preferably, the time for the third flocculation in step (3) is 20-30min, such as 20min, 20.5min, 21min, 21.5min, 22min, 22.5min, 23min, 23.5min, 24min, 24.5min, 25min, 25.5min, 26min, 26.5min, 27min, 27.5min, 28min, 28.5min, 29min, 29.5min or 30min, etc., but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the surface load is controlled to be less than 1.5m in the fourth solid-liquid separation in the step (3) 3 /(m 2 H) may be, for example, 1.4m 3 /(m 2 ·h)、1.3m 3 /(m 2 ·h)、1.2m 3 /(m 2 ·h)、1.1m 3 /(m 2 ·h)、1.0m 3 /(m 2 ·h)、0.9m 3 /(m 2 ·h)、0.8m 3 /(m 2 ·h)、0.7m 3 /(m 2 ·h)、0.6m 3 /(m 2 ·h)、0.5m 3 /(m 2 ·h)、0.4m 3 /(m 2 ·h)、0.3m 3 /(m 2 H) or 0.2m 3 /(m 2 H) and the like, but are not limited to the values recited, and other values not recited within the range are equally applicable.
As a preferable technical scheme of the invention, the purification method comprises the following steps:
(1) adding a ferrous salt solution into the nickel plating wastewater for pretreatment, then sequentially carrying out first pH adjustment, first coagulation, first flocculation and first solid-liquid separation, adding an oxidant into the obtained liquid phase for strengthening reaction, and then sequentially carrying out reduction, second pH value adjustment, second coagulation, second flocculation and second solid-liquid separation to obtain a primary treatment solution; the mass concentration of the ferrite solution is 10-12%, and the addition amount is 8-9 per mill of the volume of the nickel plating wastewater; the pretreatment time is 40-50 min; the final pH value of the first pH value adjustment is 11-11.5, and the first coagulation is carried out after the final pH value is reached and the temperature is kept for 15-20 min; a sulfide solution and a coagulant solution are added into the first coagulation, the addition amount of the sulfide solution is 2-3 per mill of the volume of the nickel plating wastewater, the mass concentration of the sulfide solution is 5-6%, the addition amount of the coagulant solution is 2-3 per mill of the volume of the nickel plating wastewater, the mass concentration of the coagulant solution is 5-6%, and the time of the first coagulation is 20-30 min; the addition amount of the flocculant solution in the first flocculation is 5-6 per mill of the volume of the nickel plating wastewater, the concentration of the flocculant solution is 0.2-0.3%, and the time of the first flocculation is 20-30 min; the surface load is controlled to be less than 1.5m in the first solid-liquid separation 3 /(m 2 H); the oxidant comprises a chlorine-containing oxidant solution with the mass concentration of 10-12%, the addition amount is 10-12 per mill of the volume of the nickel plating wastewater, and the time of the enhanced reaction is 4-8 h; the addition amount of the reducing agent with the mass concentration of 10-12% in the reduction is 8-9 per mill of the volume of the nickel plating wastewater, and the reduction time is 30-40 min; the final pH value of the second pH value adjustment is 11-11.5, and the second coagulation is carried out after the final pH value is reached and the temperature is kept for 15-20 min; a sulfide solution and a coagulant solution are added into the second coagulation, the mass concentration of the sulfide solution is 5-6%, the mass concentration of the coagulant solution is 5-6%, the addition amount of the sulfide solution is 3-4 per mill of the volume of the nickel plating wastewater, the addition amount of the coagulant solution is 3-4 per mill of the volume of the nickel plating wastewater, and the coagulation time is 20-30 min; the addition amount of the flocculating agent with the mass concentration of 0.2-0.3 percent used in the second flocculation is the nickel plating wastewater body5-6 per mill of the product, and the flocculation time is 20-30 min; controlling the surface load to be less than 1m in the second solid-liquid separation 3 /(m 2 ·h)；
(2) The primary treatment liquid obtained in the step (1) is subjected to third pH value adjustment, and then A is sequentially carried out 2 Performing O treatment and AO treatment, and then performing third solid-liquid separation to obtain secondary treatment liquid; the final pH value of the third pH value adjustment is 8.8-9.3, and the third pH value adjustment is kept for 30-40min after the final pH value is reached for A 2 O treatment; a is described 2 The O treatment comprises hydrolysis acidification, primary denitrification and primary nitrification which are sequentially carried out, wherein the hydrolysis acidification is carried out for 15-20h, the addition amount of a glucose solution with the mass concentration of 5-6% used in the primary denitrification is 1-2 per mill of the volume of the nickel plating wastewater, the primary denitrification time is 5-8h, and the primary nitrification time is 8-12 h; the AO treatment comprises secondary denitrification and secondary nitrification which are sequentially carried out, wherein the addition amount of a glucose solution with the mass concentration of 5-6% used in the secondary denitrification is 3-4 per mill of the volume of the nickel plating wastewater, the time of the secondary denitrification is 3-5h, and the time of the secondary nitrification is 6-8 h; controlling the surface load to be less than 1m in the third solid-liquid separation 3 /(m 2 ·h)；
(3) Performing fourth pH value adjustment on the secondary treatment liquid obtained in the step (2), and then sequentially performing Fenton treatment, fifth pH value adjustment, third coagulation, third flocculation and fourth solid-liquid separation to obtain discharge water; the end point pH value of the fourth pH value adjustment is 3.3-3.8, and after the end point pH value is reached, the Fenton treatment is carried out for 15-20 min; adding 10-12% ferrous salt solution and 28-30% hydrogen peroxide solution in the Fenton treatment, wherein the addition amount of the ferrous salt solution is 6-7 per mill of the volume of the nickel plating wastewater, the addition amount of the hydrogen peroxide is 1-2 per mill of the volume of the nickel plating wastewater, and the Fenton treatment time is 2-6 hours; the final pH value of the fifth pH value adjustment is 11-11.5, and the final pH value is maintained for 15-20min for third coagulation; sulfide solution with the mass concentration of 5-6% and coagulant solution with the mass concentration of 5-6% are added into the third coagulation, the addition amount of the sulfide solution is 1-2 per mill of the volume of the nickel plating wastewater, and the addition amount of the coagulant solution is 1-2 per mill of the volume of the nickel plating wastewater1-2 per mill of the volume of the nickel plating wastewater, and the time for third coagulation is 20-30 min; the addition amount of a flocculating agent with the mass concentration of 0.2-0.3% in the third flocculation is 6-7 per mill of the volume of the nickel plating wastewater, and the time of the third flocculation is 20-30 min; the surface load is controlled to be less than 1.5m in the fourth solid-liquid separation 3 /(m 2 ·h)。
In the present invention, the ferrous salt may be ferrous chloride, ferrous sulfate, ferrous nitrate or other ferrous salts commonly used in the art.
In the present invention, the sulfide may be sodium sulfide, potassium sulfide, hydrogen sulfide, etc. or other sulfides commonly used in the art.
In the present invention, the reducing agent may be sodium bisulfite or other reducing agents commonly used in the art.
In the invention, the chlorine-containing oxidant can be bleaching water, sodium hypochlorite solution, hypochlorous acid solution and the like.
In the present invention, the coagulant used may be an inorganic polymeric flocculant, such as PAC, PAS, or the like.
In the invention, the flocculant can be a nonionic polymeric flocculant PAM and the like.
In the invention, the fourth solid-liquid separation is carried out to obtain the discharged water with Ni less than or equal to 0.12mg/L, and the pH value of the discharged water also needs to be adjusted, wherein the adjustment can be carried out according to the actual requirement, for example, the discharged water is adjusted to be the proper pH value when the discharged water is used as the return water.
Compared with the prior art, the invention at least has the following beneficial effects:
(1) the process has good stability and strong impact resistance, the nickel content in the discharged water can stably reach less than or equal to 0.12mg/L, the total copper content is less than or equal to 0.18mg/L, the COD content is less than or equal to 41mg/L, the total phosphorus content is less than or equal to 0.58mg/L, the total nitrogen content is less than or equal to 18.74mg/L, and the ammonia nitrogen content is less than or equal to 0.88 mg/L.
(2) The effluent of the process can enter a clear water discharge tank to be directly discharged after reaching standards, and does not need to enter other wastewater treatment systems for treatment.
(3) The process has the advantages of low investment cost, moderate operation cost, simple process control parameters, simple daily operation, strong practicability and good stability, and ensures the normal and stable production of the sewage station.
Detailed Description
To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows:
example 1
The embodiment provides a method for purifying nickel plating wastewater, which comprises the following steps:
(1) adding a ferrous salt solution into the nickel plating wastewater for pretreatment, then sequentially carrying out first pH adjustment, first coagulation, first flocculation and first solid-liquid separation, adding an oxidant into the obtained liquid phase for strengthening reaction, and then sequentially carrying out reduction, second pH value adjustment, second coagulation, second flocculation and second solid-liquid separation to obtain a primary treatment solution; the mass concentration of the ferrous salt solution (ferrous sulfate) is 11%, and the addition amount is 8.6 per mill of the volume of the nickel plating wastewater; the pretreatment time is 45 min; the end point pH value of the first pH value adjustment is 11.2, the first coagulation is carried out after the end point pH value is reached and is kept for 17min, and the pH adjustment is carried out by adopting calcium oxide; a sulfide solution (sodium sulfide) and a coagulant solution (PAC) are added into the first coagulation, the addition amount of the sulfide solution is 2.5 per mill of the volume of the nickel plating wastewater, the mass concentration of the sulfide solution is 5.5%, the addition amount of the coagulant solution is 2.5 per mill of the volume of the nickel plating wastewater, the mass concentration of the coagulant solution is 5.5%, and the time of the first coagulation is 25 min; the addition amount of a flocculant solution (PAM) in the first flocculation is 5.5 per mill of the volume of the nickel plating wastewater, the concentration of the flocculant solution is 0.25 percent, and the time of the first flocculation is 25 min; the surface load in the first solid-liquid separation is controlled to be 1.4m 3 /(m 2 H) separation in a sedimentation tank; the oxidant comprises a chlorine-containing oxidant solution (bleaching water) with the mass concentration of 11%, the addition amount of the chlorine-containing oxidant solution is 11 per mill of the volume of the nickel plating wastewater, and the time of the enhanced reaction is 6 hours; the addition amount of the reducing agent (sodium bisulfite) with the mass concentration of 11 percent in the reduction is 8.6 per mill of the volume of the nickel plating wastewater, and the reduction time is 34 min; the end point pH of the second pH adjustment is 11.2, and the end point is reachedKeeping the pH value for 18min for secondary coagulation, and adjusting the pH value by adopting calcium oxide; a sulfide solution (sodium sulfide) and a coagulant solution (PAC) are added into the second coagulation, the mass concentration of the sulfide solution is 5.4%, the mass concentration of the coagulant solution is 5.6%, the addition amount of the sulfide solution is 3.4 per mill of the volume of the nickel plating wastewater, the addition amount of the coagulant solution is 3.6 per mill of the volume of the nickel plating wastewater, and the coagulation time is 26 min; the addition amount of a flocculating agent (PAM) with the mass concentration of 0.25 percent used in the second flocculation is 5.4 per mill of the volume of the nickel plating wastewater, and the flocculation time is 24 min; controlling the surface load to be 0.6m in the second solid-liquid separation 3 /(m 2 H) in a sedimentation tank;
(2) the primary treatment liquid obtained in the step (1) is subjected to third pH value adjustment, and then A is sequentially carried out 2 Performing O treatment and AO treatment, and then performing third solid-liquid separation to obtain secondary treatment liquid; the final pH value of the third pH value adjustment is 9, and the third pH value adjustment is carried out after the final pH value is reached and is kept for 34min for A 2 O treatment; a is described 2 The O treatment comprises hydrolysis acidification, primary denitrification and primary nitrification which are sequentially carried out, wherein the hydrolysis acidification is carried out for 18 hours, the addition amount of a glucose solution with the mass concentration of 5.6 percent used in the primary denitrification is 1.6 per mill of the volume of the nickel plating wastewater, the primary denitrification is carried out for 6 hours, and the primary nitrification is carried out for 10 hours; the AO treatment comprises secondary denitrification and secondary nitrification which are sequentially carried out, wherein the addition amount of a glucose solution with the mass concentration of 5.5 percent used in the secondary denitrification is 3.4 per mill of the volume of the nickel plating wastewater, the time of the secondary denitrification is 4 hours, and the time of the secondary nitrification is 7 hours; the surface load in the third solid-liquid separation is controlled to be 0.1m 3 /(m 2 H) in a sedimentation tank;
(3) performing fourth pH value adjustment on the secondary treatment liquid obtained in the step (2), and then sequentially performing Fenton treatment, fifth pH value adjustment, third coagulation, third flocculation and fourth solid-liquid separation to obtain discharge water; the end point pH value of the fourth pH value adjustment is 3.5, and after the end point pH value is reached, the Fenton treatment is carried out for 18 min; the Fenton treatment is added with 11% ferrous salt solution (ferrous sulfate) and substanceHydrogen peroxide solution with the quantitative concentration of 29 percent, wherein the addition amount of the ferrite solution is 6.5 per mill of the volume of the nickel plating wastewater, the addition amount of the hydrogen peroxide is 1.5 per mill of the volume of the nickel plating wastewater, and the Fenton treatment time is 4 hours; the final pH value of the fifth pH value adjustment is 11.2, the third coagulation is carried out after the final pH value is reached and is kept for 18min, and the pH adjustment is carried out by adopting calcium oxide; a sulfide solution (sodium sulfide) with the mass concentration of 5.4% and a coagulant (PAC) solution with the mass concentration of 5.6% are added into the third coagulation, the addition amount of the sulfide solution is 1.4 per mill of the volume of the nickel plating wastewater, the addition amount of the coagulant solution is 1.7 per mill of the volume of the nickel plating wastewater, and the time of the third coagulation is 25 min; in the third flocculation, the addition amount of a flocculating agent (PAM) with the mass concentration of 0.25% is 6.6 per mill of the volume of the nickel plating wastewater, and the time of the third flocculation is 24 min; the surface load in the fourth solid-liquid separation is controlled to be 1.1m 3 /(m 2 H), the treatment is carried out in a sedimentation tank.
The liquid phase composition at each stage during the treatment is detailed in table 1.
Example 2
The embodiment provides a method for purifying nickel plating wastewater, which comprises the following steps:
(1) adding a ferrous salt solution into the nickel plating wastewater for pretreatment, then sequentially carrying out first pH adjustment, first coagulation, first flocculation and first solid-liquid separation, adding an oxidant into the obtained liquid phase for strengthening reaction, and then sequentially carrying out reduction, second pH value adjustment, second coagulation, second flocculation and second solid-liquid separation to obtain a primary treatment solution; the mass concentration of the ferrous salt solution (ferrous sulfate) is 10%, and the addition amount is 8 per mill of the volume of the nickel plating wastewater; the pretreatment time is 50 min; the end point pH value of the first pH value adjustment is 11, the first coagulation is carried out after the end point pH value is reached and is kept for 15min, and the pH adjustment is carried out by adopting calcium oxide; a sulfide solution (potassium sulfide) and a coagulant solution (PAS) are added into the first coagulation, the addition amount of the sulfide solution is 2 per mill of the volume of the nickel plating wastewater, the mass concentration of the sulfide solution is 6 percent, and the mixing is carried outThe addition amount of the coagulant solution is 3 per mill of the volume of the nickel plating wastewater, the mass concentration of the coagulant solution is 5 percent, and the first coagulation time is 20 min; the addition amount of a flocculating agent (PAM) solution in the first flocculation is 6 per mill of the volume of the nickel plating wastewater, the concentration of the flocculating agent solution is 0.2 percent, and the time of the first flocculation is 20 min; controlling the surface load to be 1.2m in the first solid-liquid separation 3 /(m 2 H) in a sedimentation tank; the oxidant comprises a chlorine-containing oxidant solution (sodium hypochlorite solution) with the mass concentration of 10%, the addition amount of the oxidant is 12 per mill of the volume of the nickel plating wastewater, and the time of the enhanced reaction is 4 hours; the addition amount of the reducing agent (sodium sulfite) with the mass concentration of 10 percent in the reduction is 8 per mill of the volume of the nickel plating wastewater, and the reduction time is 30 min; the end point pH value of the second pH value adjustment is 11, the second coagulation is carried out after the end point pH value is reached and is kept for 15min, and the pH adjustment is carried out by adopting calcium oxide; a sulfide solution (sodium sulfide) and a coagulant solution (PAS) are added into the second coagulation, the mass concentration of the sulfide solution is 5%, the mass concentration of the coagulant solution is 6%, the addition amount of the sulfide solution is 3 per mill of the volume of the nickel plating wastewater, the addition amount of the coagulant solution is 4 per mill of the volume of the nickel plating wastewater, and the coagulation time is 20 min; the addition amount of a flocculating agent (PAM) with the mass concentration of 0.2% used in the second flocculation is 6 per mill of the volume of the nickel plating wastewater, and the flocculation time is 20 min; controlling the surface load to be 0.75m in the second solid-liquid separation 3 /(m 2 H) in a sedimentation tank;
(2) the primary treatment liquid obtained in the step (1) is subjected to third pH value adjustment, and then A is sequentially carried out 2 Performing O treatment and AO treatment, and then performing third solid-liquid separation to obtain secondary treatment liquid; the final pH value of the third pH value adjustment is 8.8, and the third pH value adjustment is kept for 30min after the final pH value is reached to carry out A 2 O treatment; a is described 2 The O treatment comprises hydrolysis acidification, primary denitrification and primary nitrification which are sequentially carried out, wherein the hydrolysis acidification is carried out for 15 hours, the addition amount of a glucose solution with the mass concentration of 5% in the primary denitrification is 1 per mill of the volume of the nickel plating wastewater, the primary denitrification is carried out for 5 hours, and the primary nitrification is carried out for 12 hours;the AO treatment comprises secondary denitrification and secondary nitrification which are sequentially carried out, wherein the addition amount of a glucose solution with the mass concentration of 5% used in the secondary denitrification is 4 per mill of the volume of the nickel plating wastewater, the time of the secondary denitrification is 3 hours, and the time of the secondary nitrification is 6 hours; the surface load in the third solid-liquid separation is controlled to be 0.46m 3 /(m 2 H) in a sedimentation tank;
(3) performing fourth pH value adjustment on the secondary treatment liquid obtained in the step (2), and then sequentially performing Fenton treatment, fifth pH value adjustment, third coagulation, third flocculation and fourth solid-liquid separation to obtain discharge water; the end point pH value of the fourth pH value adjustment is 3.3, and the Fenton treatment is carried out after the end point pH value is reached and the pH value is kept for 20 min; adding a ferrous salt solution (ferrous chloride) with the mass concentration of 12% and a hydrogen peroxide solution with the mass concentration of 28% in the Fenton treatment, wherein the addition amount of the ferrous salt solution is 7 per mill of the volume of the nickel plating wastewater, the addition amount of the hydrogen peroxide is 1 per mill of the volume of the nickel plating wastewater, and the time of the Fenton treatment is 6 hours; the final pH value of the fifth pH value adjustment is 11.5, the third coagulation is carried out after the final pH value is reached and is kept for 20min, and the pH adjustment is carried out by adopting calcium oxide; a sulfide solution (sodium sulfide) with the mass concentration of 5% and a coagulant solution (PAC) with the mass concentration of 6% are added into the third coagulation, the addition amount of the sulfide solution is 2 per mill of the volume of the nickel plating wastewater, the addition amount of the coagulant solution is 1 per mill of the volume of the nickel plating wastewater, and the time of the third coagulation is 20 min; the addition amount of a flocculating agent (PAM) with the mass concentration of 0.3% in the third flocculation is 7 per mill of the volume of the nickel plating wastewater, and the time of the third flocculation is 30 min; the surface load in the fourth solid-liquid separation is controlled to be 0.75m 3 /(m 2 H), the treatment is carried out in a sedimentation tank.
The liquid phase composition at each stage during the treatment is detailed in table 1.
Example 3
The embodiment provides a method for purifying nickel plating wastewater, which comprises the following steps:
(1) adding ferrous salt solution into nickel plating wastewaterPretreating the liquid, sequentially carrying out first pH adjustment, first coagulation, first flocculation and first solid-liquid separation, adding an oxidant into the obtained liquid phase for a strengthening reaction, and sequentially carrying out reduction, second pH adjustment, second coagulation, second flocculation and second solid-liquid separation to obtain a primary treatment liquid; the mass concentration of the ferrous salt solution (ferrous sulfate) is 12%, and the addition amount is 9 per mill of the volume of the nickel plating wastewater; the pretreatment time is 40 min; the terminal pH value of the first pH value adjustment is 11.5, the first coagulation is carried out after the terminal pH value is reached and is kept for 20min, and the pH value adjustment is carried out by adopting calcium oxide; a sulfide solution (sodium hydrosulfide) and a coagulant solution (PAC) are added into the first coagulation, the addition amount of the sulfide solution is 3 per mill of the volume of the nickel plating wastewater, the mass concentration of the sulfide solution is 5 percent, the addition amount of the coagulant solution is 2 per mill of the volume of the nickel plating wastewater, the mass concentration of the coagulant solution is 6 percent, and the time of the first coagulation is 30 min; the addition amount of a flocculant solution (PAM) in the first flocculation is 5 per mill of the volume of the nickel plating wastewater, the concentration of the flocculant solution is 0.3 percent, and the time of the first flocculation is 30 min; the surface load in the first solid-liquid separation is controlled to be 0.5m 3 /(m 2 H) in a sedimentation tank; the oxidant comprises a chlorine-containing oxidant solution (hypochlorous acid solution) with the mass concentration of 12%, the addition amount of the chlorine-containing oxidant solution is 10 per mill of the volume of the nickel plating wastewater, and the time of the enhanced reaction is 8 hours; the addition amount of the reducing agent (potassium sulfite) with the mass concentration of 12% in the reduction is 9 per mill of the volume of the nickel plating wastewater, and the reduction time is 40 min; the end point pH value of the second pH value adjustment is 11.5, the second coagulation is carried out after the end point pH value is reached and is kept for 20min, and the pH adjustment is carried out by adopting calcium oxide; a sulfide solution (potassium sulfide) and a coagulant solution (PFS) are added into the second coagulation, the mass concentration of the sulfide solution is 6%, the mass concentration of the coagulant solution is 5%, the addition amount of the sulfide solution is 4 per mill of the volume of the nickel-plating wastewater, the addition amount of the coagulant solution is 3 per mill of the volume of the nickel-plating wastewater, and the coagulation time is 30 min; the addition amount of a flocculant (PAM) having a mass concentration of 0.3% used in the second flocculation is the amount of the plating solutionThe flocculation time is 30min and is 5 per mill of the volume of the nickel wastewater; controlling the surface load to be 0.35m in the second solid-liquid separation 3 /(m 2 H) in a sedimentation tank;
(2) the primary treatment liquid obtained in the step (1) is subjected to third pH value adjustment, and then A is sequentially carried out 2 Performing O treatment and AO treatment, and then performing third solid-liquid separation to obtain secondary treatment liquid; the final pH value of the third pH value adjustment is 9.3, and the third pH value adjustment is kept for 40min after the final pH value is reached 2 O treatment; a is described 2 The O treatment comprises hydrolysis acidification, primary denitrification and primary nitrification which are sequentially carried out, wherein the hydrolysis acidification is carried out for 20 hours, the addition amount of a glucose solution with the mass concentration of 6 percent used in the primary denitrification is 2 per mill of the volume of the nickel plating wastewater, the primary denitrification is carried out for 8 hours, and the primary nitrification is carried out for 8 hours; the AO treatment comprises secondary denitrification and secondary nitrification which are sequentially carried out, wherein the addition amount of a glucose solution with the mass concentration of 6% used in the secondary denitrification is 3 per mill of the volume of the nickel plating wastewater, the time of the secondary denitrification is 5 hours, and the time of the secondary nitrification is 8 hours; the surface load in the third solid-liquid separation is controlled to be 0.67m 3 /(m 2 H) in a sedimentation tank;
(3) performing fourth pH value adjustment on the secondary treatment liquid obtained in the step (2), and then sequentially performing Fenton treatment, fifth pH value adjustment, third coagulation, third flocculation and fourth solid-liquid separation to obtain discharge water; the end point pH value of the fourth pH value adjustment is 3.8, and the Fenton treatment is carried out after the end point pH value is reached and the pH value is kept for 15 min; adding 10% ferrous salt solution (ferrous sulfate) and 30% hydrogen peroxide solution in the Fenton treatment, wherein the addition amount of the ferrous salt solution is 6 per mill of the volume of the nickel plating wastewater, the addition amount of the hydrogen peroxide is 2 per mill of the volume of the nickel plating wastewater, and the time of the Fenton treatment is 2 hours; the final pH value of the fifth pH value adjustment is 11, the third coagulation is carried out after the final pH value is reached and is kept for 15min, and the pH adjustment is carried out by adopting calcium oxide; a sulfide solution (sodium hydrogen sulfide) with a mass concentration of 6% and a coagulant solution (PPAC) with a mass concentration of 5% are added in the third coagulation, and the addition amount of the sulfide solution1 per mill of the volume of the nickel plating wastewater, 2 per mill of the volume of the nickel plating wastewater and 30min of third coagulation; in the third flocculation, the addition amount of a flocculating agent (PAM) with the mass concentration of 0.2% is 6 per mill of the volume of the nickel plating wastewater, and the time of the third flocculation is 20 min; the surface load in the fourth solid-liquid separation is controlled to be 0.54m 3 /(m 2 H) in a sedimentation basin.
The liquid phase composition at each stage during the treatment is detailed in table 1.
Example 4
The only difference from example 1 is that the strengthening reaction and the Fenton treatment are exchanged, i.e., the Fenton treatment is used in step (1) and then the strengthening reaction is performed in step (3). The composition of the liquid phase at each stage during the treatment is detailed in Table 1.
Example 5
Only differs from example 1 in that A is not carried out 2 AO after O. The liquid phase composition at each stage during the treatment is detailed in table 1.
Example 6
The only difference from example 1 is that the fenton treatment in step (3) is replaced with the strengthening reaction in step (1), i.e., 2 strengthening reactions are performed, and the strengthening reactions are performed in both step (1) and step (3). The liquid phase composition at each stage during the treatment is detailed in table 1.
Example 7
The only difference from example 1 is that the fenton treatment in step (3) is replaced by the pretreatment in step (1), i.e., 2 pretreatments are performed, and the pretreatment is performed in both step (1) and step (3). The composition of the liquid phase at each stage during the treatment is detailed in Table 1.
Example 8
The only difference from example 1 is that the pretreatment in step (1) is replaced with the fenton treatment in step (3), that is, 2 fenton treatments are performed, and the fenton treatments are performed in both step (1) and step (3). The liquid phase composition at each stage during the treatment is detailed in table 1.
Example 9
The only difference from example 1 is that the strengthening reaction in step (1) is replaced with fenton treatment in step (3), i.e., 2 fenton treatments are performed, and the fenton treatments are performed in both step (1) and step (3). The liquid phase composition at each stage during the treatment is detailed in table 1.
Example 10
The only difference from example 1 is that the pretreatment in step (1) is replaced by the strengthening reaction in step (1), i.e., step (1) is carried out 2 consecutive times of strengthening reactions. The liquid phase composition at each stage during the treatment is detailed in table 1.
Example 11
The only difference from example 1 is that the strengthening reaction in step (1) is replaced by pretreatment in step (1), i.e., step (1) is subjected to 2 consecutive pretreatments. The liquid phase composition at each stage during the treatment is detailed in table 1.
TABLE 1
The composition of the main pollutants of the nickel plating wastewater used in the above examples was as follows: total copper: 61mg/L, total nickel 87mg/L, COD543mg/L, total phosphorus 317mg/L, total nitrogen 344mg/L, ammonia nitrogen 177 mg/L.
According to the results of the embodiment, the nickel plating wastewater treatment system adopts a specific purification process to ensure that the outlet water can enter the clear water discharge tank to be directly discharged up to the standard without entering other wastewater treatment systems for treatment. The method has the advantages of low construction investment cost, moderate operation cost, simple process control parameters, simple daily operation, strong practicability, good stability and capability of ensuring normal and stable production of the sewage station.
It is to be noted that the present invention is described by the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the detailed structural features, that is, it is not meant to imply that the present invention must be implemented by relying on the detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. A method for purifying nickel plating wastewater is characterized by comprising the following steps:
(1) adding a ferrous salt solution into the nickel plating wastewater for pretreatment, then sequentially carrying out first pH adjustment, first coagulation, first flocculation and first solid-liquid separation, adding an oxidant into the obtained liquid phase for strengthening reaction, and then sequentially carrying out reduction, second pH value adjustment, second coagulation, second flocculation and second solid-liquid separation to obtain a primary treatment solution;
(2) carrying out the primary treatment liquid obtained in the step (1)A third pH adjustment is carried out, and then A is carried out in sequence 2 Performing O treatment and AO treatment, and then performing third solid-liquid separation to obtain secondary treatment liquid;
(3) and (3) performing fourth pH value adjustment on the secondary treatment liquid obtained in the step (2), and then sequentially performing Fenton treatment, fifth pH value adjustment, third coagulation, third flocculation and fourth solid-liquid separation to obtain discharge water.
2. The purification method of claim 1, wherein the ferrous salt solution of step (1) has a mass concentration of 10-12%;
preferably, the addition amount of the ferrous salt solution in the step (1) is 8-9 per mill of the volume of the nickel plating wastewater;
preferably, the pretreatment time of the step (1) is 40-50 min;
preferably, the end point pH of the first pH adjustment of step (1) is 11-11.5;
preferably, the first coagulation is carried out by keeping for 15-20min after the first pH value adjustment in the step (1) reaches the end point pH value.
3. The purification method according to claim 1 or 2, wherein a sulfide solution and a coagulant solution are added to the first coagulation in step (1);
preferably, the addition amount of the sulfide solution used in the first coagulation in the step (1) is 2-3 per mill of the volume of the nickel plating wastewater;
preferably, the mass concentration of the sulfide solution used in the first coagulation in the step (1) is 5-6%;
preferably, the addition amount of the coagulant solution used in the first coagulation in the step (1) is 2-3 per mill of the volume of the nickel plating wastewater;
preferably, the mass concentration of the coagulant solution used in the first coagulation in the step (1) is 5-6%;
preferably, the time of the first coagulation in the step (1) is 20-30 min;
preferably, the addition amount of the flocculant solution used in the first flocculation in the step (1) is 5-6 per mill of the volume of the nickel plating wastewater;
preferably, the concentration of the flocculant solution used in the first flocculation in step (1) is 0.2-0.3%;
preferably, the time of the first flocculation in the step (1) is 20-30 min;
preferably, the surface load is controlled to be less than 1.5m in the first solid-liquid separation in the step (1) 3 /(m 2 ·h)。
4. The purification process of any one of claims 1-3, wherein the oxidizing agent of step (1) comprises a chlorine-containing oxidizing agent solution;
preferably, the adding amount of the oxidant in the step (1) is 10-12 per mill of the volume of the nickel plating wastewater;
preferably, the mass concentration of the oxidant in the step (1) is 10-12%;
preferably, the strengthening reaction time of the step (1) is 4-8 h;
preferably, the addition amount of the reducing agent used in the reduction in the step (1) is 8-9 per mill of the volume of the nickel plating wastewater;
preferably, the mass concentration of the reducing agent used in the reduction in the step (1) is 10-12%;
preferably, the reduction time of the step (1) is 30-40 min;
preferably, the end point pH of the second pH adjustment of step (1) is 11-11.5;
preferably, the second coagulation is carried out by keeping for 15-20min after the second pH value adjustment of the step (1) reaches the end point pH value.
5. The purification method according to any one of claims 1 to 4, wherein a sulfide solution and a coagulant solution are added to the second coagulation in step (1);
preferably, the mass concentration of the sulfide solution used in the second coagulation in the step (1) is 5-6%;
preferably, the addition amount of the sulfide solution used in the second coagulation in the step (1) is 3-4 per mill of the volume of the nickel plating wastewater;
preferably, the mass concentration of the coagulant solution used in the second coagulation in the step (1) is 5-6%;
preferably, the addition amount of the coagulant solution used in the second coagulation in the step (1) is 3-4 per mill of the volume of the nickel plating wastewater;
preferably, the time of the second coagulation in the step (1) is 20-30 min;
preferably, the mass concentration of the flocculating agent used in the second flocculation in the step (1) is 0.2-0.3%;
preferably, the addition amount of the flocculating agent used in the second flocculation in the step (1) is 5-6 per mill of the volume of the nickel plating wastewater;
preferably, the time of the second flocculation in the step (1) is 20-30 min;
preferably, the surface load is controlled to be less than 1m in the second solid-liquid separation in the step (1) 3 /(m 2 ·h)。
6. The purification method according to any one of claims 1 to 5, wherein the final pH of the third pH adjustment in the step (2) is 8.8 to 9.3;
preferably, the third pH value adjustment in the step (2) is carried out for 30-40min after reaching the end point pH value 2 And (4) O treatment.
7. The purification method according to any one of claims 1 to 6, wherein A in step (2) 2 The O treatment comprises hydrolysis acidification, primary denitrification and primary nitrification which are sequentially carried out;
preferably, the hydrolytic acidification is carried out for 15-20 h;
preferably, the addition amount of the glucose solution with the mass concentration of 5-6% used in the primary denitrification in the step (2) is 1-2 per mill of the volume of the nickel plating wastewater;
preferably, the time of the primary denitrification is 5-8 h;
preferably, the time of the primary nitration is 8-12 h;
preferably, the AO treatment of step (2) comprises a secondary denitrification and a secondary nitrification which are performed in sequence;
preferably, the addition amount of the glucose solution with the mass concentration of 5-6% used in the secondary denitrification is 3-4 per mill of the volume of the nickel plating wastewater;
preferably, the time of the secondary denitrification is 3-5 h;
preferably, the time of the secondary nitration is 6-8 h;
preferably, the surface load is controlled to be less than 1m in the third solid-liquid separation in the step (2) 3 /(m 2 ·h)。
8. The purification method according to any one of claims 1 to 7, wherein the fourth pH adjustment in step (3) has an end point pH of 3.3 to 3.8;
preferably, after the fourth pH value adjustment in the step (3) reaches the end point pH value, keeping for 15-20min for performing Fenton treatment;
preferably, a ferrous salt solution and a hydrogen peroxide solution are added in the fenton treatment in the step (3);
preferably, the mass concentration of the ferrous salt solution is 10-12%;
preferably, the mass concentration of the hydrogen peroxide solution is 28-30%;
preferably, the addition amount of the ferrous salt solution used in the fenton treatment in the step (3) is 6-7 per mill of the volume of the nickel plating wastewater;
preferably, the addition amount of the hydrogen peroxide used in the fenton treatment in the step (3) is 1-2 per mill of the volume of the nickel plating wastewater;
preferably, the Fenton treatment time in the step (3) is 2-6 h;
preferably, the end point pH of the fifth pH adjustment of step (3) is 11-11.5;
preferably, the fifth pH value adjustment in the step (3) is kept for 15-20min after reaching the end point pH value for carrying out third coagulation.
9. The purification method according to any one of claims 1 to 8, wherein a sulfide solution and a coagulant solution are added to the third coagulation in the step (3);
preferably, the mass concentration of the sulfide solution used in the third coagulation in the step (3) is 5-6%;
preferably, the addition amount of the sulfide solution used in the third coagulation in the step (3) is 1-2 per mill of the volume of the nickel plating wastewater;
preferably, the mass concentration of the coagulant solution used in the third coagulation in the step (3) is 5-6%;
preferably, the addition amount of the coagulant solution used in the third coagulation in the step (3) is 1-2 per mill of the volume of the nickel plating wastewater;
preferably, the time of the third coagulation in the step (3) is 20-30 min;
preferably, the addition amount of the flocculating agent used in the third flocculation in the step (3) is 6-7 per mill of the volume of the nickel plating wastewater;
preferably, the mass concentration of the flocculating agent used in the third flocculation in the step (3) is 0.2-0.3%;
preferably, the time of the third flocculation in the step (3) is 20-30 min;
preferably, the surface load is controlled to be less than 1.5m in the fourth solid-liquid separation in the step (3) 3 /(m 2 ·h)。
10. The decontamination method of any one of claims 1-9, wherein the decontamination method comprises the steps of:
(1) adding a ferrous salt solution into the nickel plating wastewater for pretreatment, then sequentially carrying out first pH adjustment, first coagulation, first flocculation and first solid-liquid separation, adding an oxidant into the obtained liquid phase for strengthening reaction, and then sequentially carrying out reduction, second pH value adjustment, second coagulation, second flocculation and second solid-liquid separation to obtain a primary treatment solution; the mass concentration of the ferrite solution is 10-12%, and the addition amount is 8-9 per mill of the volume of the nickel plating wastewater; the pretreatment time is 40-50 min; the final pH value of the first pH value adjustment is 11-11.5, and the first coagulation is carried out after the final pH value is reached and the temperature is kept for 15-20 min; sulfide solution and coagulant solution are added into the first coagulation, the addition amount of the sulfide solution is 2-3 per mill of the volume of the nickel plating wastewater, the mass concentration of the sulfide solution is 5-6%, the addition amount of the coagulant solution is 2-3 per mill of the volume of the nickel plating wastewater, the mass concentration of the coagulant solution is 5-6%, and the first coagulation is carried out in real timeThe time is 20-30 min; the addition amount of the flocculant solution in the first flocculation is 5-6 per mill of the volume of the nickel plating wastewater, the concentration of the flocculant solution is 0.2-0.3%, and the time of the first flocculation is 20-30 min; the surface load is controlled to be less than 1.5m in the first solid-liquid separation 3 /(m 2 H); the oxidant comprises a chlorine-containing oxidant solution with the mass concentration of 10-12%, the addition amount is 10-12 per mill of the volume of the nickel plating wastewater, and the time of the enhanced reaction is 4-8 h; the addition amount of the reducing agent with the mass concentration of 10-12% in the reduction is 8-9 per mill of the volume of the nickel plating wastewater, and the reduction time is 30-40 min; the final pH value of the second pH value adjustment is 11-11.5, and the second coagulation is carried out after the final pH value is reached and the temperature is kept for 15-20 min; a sulfide solution and a coagulant solution are added into the second coagulation, the mass concentration of the sulfide solution is 5-6%, the mass concentration of the coagulant solution is 5-6%, the addition amount of the sulfide solution is 3-4 per mill of the volume of the nickel plating wastewater, the addition amount of the coagulant solution is 3-4 per mill of the volume of the nickel plating wastewater, and the coagulation time is 20-30 min; the addition amount of a flocculating agent with the mass concentration of 0.2-0.3% used in the second flocculation is 5-6 per mill of the volume of the nickel plating wastewater, and the flocculation time is 20-30 min; controlling the surface load to be less than 1m in the second solid-liquid separation 3 /(m 2 ·h)；
(2) The primary treatment liquid obtained in the step (1) is subjected to third pH value adjustment, and then A is sequentially carried out 2 Performing O treatment and AO treatment, and then performing third solid-liquid separation to obtain secondary treatment liquid; the final pH value of the third pH value adjustment is 8.8-9.3, and the third pH value adjustment is kept for 30-40min after the final pH value is reached for A 2 O treatment; a is described 2 The O treatment comprises hydrolysis acidification, primary denitrification and primary nitrification which are sequentially carried out, wherein the hydrolysis acidification is carried out for 15-20h, the addition amount of a glucose solution with the mass concentration of 5-6% used in the primary denitrification is 1-2 per mill of the volume of the nickel plating wastewater, the primary denitrification time is 5-8h, and the primary nitrification time is 8-12 h; the AO treatment comprises secondary denitrification and secondary nitrification which are sequentially carried out, wherein the addition amount of a glucose solution with the mass concentration of 5-6% used in the secondary denitrification is 3-4 per mill of the volume of the nickel plating wastewater, and the secondary denitrificationThe time is 3-5h, and the time of the secondary nitration is 6-8 h; controlling the surface load to be less than 1m in the third solid-liquid separation 3 /(m 2 ·h)；
(3) Performing fourth pH value adjustment on the secondary treatment liquid obtained in the step (2), and then sequentially performing Fenton treatment, fifth pH value adjustment, third coagulation, third flocculation and fourth solid-liquid separation to obtain discharge water; the end point pH value of the fourth pH value adjustment is 3.3-3.8, and after the end point pH value is reached, the Fenton treatment is carried out for 15-20 min; adding 10-12% ferrous salt solution and 28-30% hydrogen peroxide solution in the Fenton treatment, wherein the addition amount of the ferrous salt solution is 6-7 per mill of the volume of the nickel plating wastewater, the addition amount of the hydrogen peroxide is 1-2 per mill of the volume of the nickel plating wastewater, and the Fenton treatment time is 2-6 hours; the final pH value of the fifth pH value adjustment is 11-11.5, and the final pH value is maintained for 15-20min for third coagulation; a sulfide solution with the mass concentration of 5-6% and a coagulant solution with the mass concentration of 5-6% are added into the third coagulation, the addition amount of the sulfide solution is 1-2 per mill of the volume of the nickel plating wastewater, the addition amount of the coagulant solution is 1-2 per mill of the volume of the nickel plating wastewater, and the time of the third coagulation is 20-30 min; the addition amount of a flocculating agent with the mass concentration of 0.2-0.3% in the third flocculation is 6-7 per mill of the volume of the nickel plating wastewater, and the time of the third flocculation is 20-30 min; the surface load is controlled to be less than 1.5m in the fourth solid-liquid separation 3 /(m 2 ·h)。
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