CN116835827A - Method for zero discharge treatment of sintering acid making wastewater - Google Patents
Method for zero discharge treatment of sintering acid making wastewater Download PDFInfo
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- CN116835827A CN116835827A CN202311043929.8A CN202311043929A CN116835827A CN 116835827 A CN116835827 A CN 116835827A CN 202311043929 A CN202311043929 A CN 202311043929A CN 116835827 A CN116835827 A CN 116835827A
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- 239000002351 wastewater Substances 0.000 title claims abstract description 112
- 238000000034 method Methods 0.000 title claims abstract description 63
- 238000005245 sintering Methods 0.000 title claims abstract description 37
- 239000002253 acid Substances 0.000 title claims abstract description 22
- 208000028659 discharge Diseases 0.000 title abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 138
- 230000008569 process Effects 0.000 claims abstract description 34
- 150000003839 salts Chemical class 0.000 claims abstract description 28
- 239000000126 substance Substances 0.000 claims abstract description 26
- 238000002425 crystallisation Methods 0.000 claims abstract description 23
- 230000008025 crystallization Effects 0.000 claims abstract description 23
- 239000012528 membrane Substances 0.000 claims abstract description 21
- 230000009615 deamination Effects 0.000 claims abstract description 20
- 238000006481 deamination reaction Methods 0.000 claims abstract description 20
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 12
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 12
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000002500 ions Chemical class 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 238000001728 nano-filtration Methods 0.000 claims description 48
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 29
- 238000001704 evaporation Methods 0.000 claims description 26
- 230000008020 evaporation Effects 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 21
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 18
- 229910052753 mercury Inorganic materials 0.000 claims description 18
- 238000001471 micro-filtration Methods 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- 238000005189 flocculation Methods 0.000 claims description 12
- 230000016615 flocculation Effects 0.000 claims description 12
- -1 fluorine ions Chemical class 0.000 claims description 12
- 239000010802 sludge Substances 0.000 claims description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 11
- 238000006115 defluorination reaction Methods 0.000 claims description 11
- 239000003546 flue gas Substances 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 10
- 229910001385 heavy metal Inorganic materials 0.000 claims description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 9
- 239000011575 calcium Substances 0.000 claims description 9
- 229910052791 calcium Inorganic materials 0.000 claims description 9
- 238000001223 reverse osmosis Methods 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 8
- 239000011737 fluorine Substances 0.000 claims description 7
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 6
- 229910001424 calcium ion Inorganic materials 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000012452 mother liquor Substances 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- 239000013505 freshwater Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000001502 supplementing effect Effects 0.000 abstract description 3
- 229920005989 resin Polymers 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 239000003344 environmental pollutant Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 231100000719 pollutant Toxicity 0.000 description 8
- 238000005273 aeration Methods 0.000 description 6
- 239000000428 dust Substances 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229920001429 chelating resin Polymers 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- 208000005156 Dehydration Diseases 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000009770 conventional sintering Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- USGMTXBBTJRWQS-UHFFFAOYSA-N mercury;dihydrate Chemical compound O.O.[Hg] USGMTXBBTJRWQS-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/048—Purification of waste water by evaporation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/463—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrocoagulation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved 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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/583—Treatment of water, waste water, or sewage by removing specified dissolved compounds by removing fluoride or fluorine 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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/18—Nature of the water, waste water, sewage or sludge to be treated from the purification of gaseous effluents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The application belongs to the technical field of water treatment, and particularly relates to a method for zero discharge treatment of sintering acid making wastewater, which comprises the following steps: chemical pretreatment for pretreating the wastewater to reduce ions in the sintering acid-making wastewater; deamination treatment for removing ammonia nitrogen in wastewater; and (3) performing evaporative crystallization treatment, namely performing membrane separation treatment on the wastewater to obtain industrial new water and concentrated water, and performing evaporative crystallization treatment on the concentrated water to obtain industrial salt. After the treatment process, the produced reuse water meets the water quality requirement of industrial new water, is taken as process supplementing water, and further obtains industrial salt products, ammonium sulfate and other products, and the whole treatment process does not produce mixed salt, thereby realizing zero emission of the treatment of the sintering acid-making wastewater.
Description
Technical Field
The application belongs to the technical field of water treatment, and particularly relates to a method for zero discharge treatment of sintering acid making wastewater.
Background
At present, sintering and pellet desulfurization and denitration flue gas is purified by adopting an active carbon flue gas purification process, and the process can simultaneously remove various pollutants such as SO2, NOx, HCl, dioxin, heavy metals, dust and the like, can recover sulfur resources to prepare a concentrated sulfuric acid product, and is a resource recovery type comprehensive flue gas treatment technology.
The saturated activated carbon is absorbed and enters a resolving tower to be highly Wen Jiexi, SO2, NOx, HCl, ammonia and the like are released in a gaseous form, some heavy metals are carried out in a dust state together with resolving gas, and resolving waste gas rich in SO2 is sent to an acid making working section to prepare sulfuric acid. In order to ensure the purity of sulfuric acid, the waste gas is washed and purified by dilute sulfuric acid before acid preparation, NH3, HCl, heavy metal ions, dust suspended matters and part of SO2 in the waste gas are transferred into dilute acid, and the acid washing wastewater discharged by the working section is acid preparation wastewater.
The wastewater has the characteristics of small water quantity, high pollutant content, complex components, large water quality change and the like, and the pollutants in the wastewater mainly comprise sulfuric acid, high-concentration NH3-N, cl-, F-, COD, suspended matters and a small amount of heavy metal ions. And has strong corrosiveness to pipelines and equipment due to high salt content and high chloride ion concentration in the treatment process. After pretreatment in a workshop, heavy metal ions in the effluent can meet the indexes required by the discharge ports of workshops or production facilities in the emission standards of water pollutants in the iron and steel industry (GB 13456-2012), but the contents of organic matters, ammonia nitrogen, chlorides, sulfate radicals, fluoride ions and the like in the wastewater are high, so that the subsequent process treatment is greatly influenced, and the residual heavy metal ions in the wastewater are not recycled.
Therefore, the application provides a method for zero discharge treatment of sintering acid making wastewater, which is used for zero discharge treatment of the wastewater. The produced reuse water meets the water quality requirement of the industrial new water, and in addition, the byproducts mainly comprise: 1) Purifying sodium chloride in the wastewater to produce industrial salt, wherein the quality of the industrial salt reaches the first-level standard of industrial dry salt of the comprehensive wastewater byproduct in the standard of comprehensive wastewater byproduct industrial salt of iron and steel enterprises; 2) A small amount of 6% ammonium sulfate. The application has high environmental protection value and economic benefit, can effectively reduce pollutant emission, recover resources and reduce environmental pollution and economic cost.
Disclosure of Invention
In order to achieve the above purpose, the application provides a method for zero discharge treatment of sintering acid making wastewater, which comprises the following steps:
chemical pretreatment for pretreating the wastewater to reduce fluorine ions, calcium ions and heavy metal ions in the sintering acid-making wastewater;
deamination treatment for removing ammonia nitrogen in wastewater;
and (3) performing evaporative crystallization treatment, namely performing membrane separation treatment on the wastewater to obtain industrial new water and concentrated water, and performing evaporative crystallization treatment on the concentrated water to obtain industrial salt.
Preferably, the evaporative crystallization process includes the steps of:
filtering to obtain industrial new water and concentrated water containing chloride ions;
the concentrated water is evaporated for obtaining industrial salt.
Preferably, the filtering process comprises the following steps;
and (3) primary nanofiltration treatment: part of chloride ions pass through the first-stage nanofiltration water to intercept sulfate ions to form first-stage concentrated water;
performing secondary nanofiltration treatment; so that part of chloride ions in the first-stage concentrated water pass through the second-stage nanofiltration water to intercept sulfate ions to form the second-stage concentrated water;
reverse osmosis treatment; and part of the solution passes through the industrial fresh water to intercept chloride ions to form tertiary concentrated water.
Preferably, after the primary nanofiltration water and the tertiary concentrated water are mixed, concentrated water evaporation treatment is carried out to obtain industrial salt.
Preferably, the filtering process further includes: and adding the evaporated condensate water to the first-stage concentrated water for dilution, and then carrying out second-stage nanofiltration treatment.
And the mother liquor generated in the evaporation treatment is refluxed and subjected to chemical pretreatment, and the chloride ion concentration of the secondary nanofiltration water after the secondary nanofiltration treatment meets the water quality requirement of flue gas cooling and spraying.
The chemical pretreatment comprises the following steps:
the electric flocculation defluorination treatment is used for removing fluorine ions in the wastewater;
calcium removal treatment for separating calcium ions in the wastewater;
and the tube-type microfiltration treatment is used for removing hardness after the calcium removal treatment.
Preferably, sludge is generated after the electric flocculation defluorination treatment and the tubular microfiltration treatment, and the sludge is sintered and mixed after being concentrated and dehydrated.
Preferably, the chemical pretreatment further comprises the steps of:
the wastewater after the tubular microfiltration treatment is subjected to hard removal treatment and mercury removal treatment in sequence;
the hardness removal treatment is used for removing residual hardness in the wastewater;
the mercury removal treatment is used for removing mercury in the wastewater.
Preferably, the deamination treatment comprises the steps of:
adding sulfuric acid into the wastewater subjected to the chemical pretreatment;
the sulfuric acid is used for removing ammonia in the wastewater and generating ammonium sulfate;
and regulating the pH value of the residual wastewater to be neutral.
In summary, the method for zero emission treatment of sintering acid-making wastewater provided by the application comprises chemical pretreatment, deamination treatment and evaporative crystallization treatment; the chemical pretreatment is used for pretreating the sintering acid making wastewater to reduce harmful heavy metal ions in the sintering acid making wastewater; the deamination treatment is used for recycling ammonia nitrogen in the sintering acid-making wastewater; the evaporation crystallization treatment is used for performing evaporation crystallization treatment on the wastewater subjected to the membrane separation treatment. After the treatment process, the produced reuse water meets the water quality requirement of industrial new water, is taken as process supplementing water, and further obtains industrial salt products, ammonium sulfate and other products, and the whole treatment process does not produce mixed salt, thereby realizing zero emission of the treatment of the sintering acid-making wastewater.
Drawings
In order to more clearly illustrate the embodiments of the application or the technical solutions in the prior art, the drawings that are necessary for the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the application and that other drawings can be obtained from them without inventive effort for a person skilled in the art.
FIG. 1 is a process flow diagram of a method for zero emission treatment of sintering acid making wastewater, which is provided by the application;
fig. 2 is a schematic flow structure diagram of a method for zero discharge treatment of sintering acid making wastewater.
Detailed Description
The application will be described in further detail with reference to the drawings and the specific embodiments thereof in order to make the objects, advantages and features of the application more apparent. It should be noted that the drawings are in a very simplified form and are not drawn to scale, merely for convenience and clarity in aiding in the description of embodiments of the application. Furthermore, the structures shown in the drawings are often part of actual structures. In particular, the drawings are shown with different emphasis instead being placed upon illustrating the various embodiments.
As used in this disclosure, the singular forms "a," "an," and "the" include plural referents, the term "or" are generally used in the sense of comprising "and/or" and the term "several" are generally used in the sense of comprising "at least one," the term "at least two" are generally used in the sense of comprising "two or more," and the term "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying any relative importance or number of features indicated. Thus, a feature defining "first," "second," "third," or "third" may explicitly or implicitly include one or at least two such features, the term "proximal" typically being one end proximal to the operator, the term "distal" typically being one end proximal to the patient, "one end" and "other" and "proximal" and "distal" typically referring to corresponding two portions, including not only the endpoints, the terms "mounted," "connected," "coupled," or "coupled" are to be construed broadly, e.g., as either a fixed connection, a removable connection, or as one piece; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communicated with the inside of two elements or the interaction relationship of the two elements. Furthermore, as used in this disclosure, an element disposed on another element generally only refers to a connection, coupling, cooperation or transmission between two elements, and the connection, coupling, cooperation or transmission between two elements may be direct or indirect through intermediate elements, and should not be construed as indicating or implying any spatial positional relationship between the two elements, i.e., an element may be in any orientation, such as inside, outside, above, below, or on one side, of the other element unless the context clearly indicates otherwise. The specific meaning of the above terms in the present application can be understood by those of ordinary skill in the art according to the specific circumstances.
The core idea of the application is to provide a method for zero discharge treatment of sintering acid-making wastewater, so as to solve the problems of small water quantity, high pollutant content, complex components, large water quality change and the like of the existing wastewater.
The following description refers to the accompanying drawings.
Referring to fig. one, the technical scheme of the process flow chart of the method for treating the wastewater generated in the acid production by sintering in a zero discharge way provided by the application comprises the following steps:
s1, chemical pretreatment is used for pretreating wastewater to reduce fluoride ions, calcium ions and heavy metal ions in sintering acid-making wastewater;
s2, deamination treatment is carried out to remove ammonia nitrogen in the wastewater;
s3, performing evaporative crystallization treatment, namely performing membrane separation treatment on the wastewater to obtain industrial new water and concentrated water, and performing evaporative crystallization treatment on the concentrated water to obtain industrial salt.
In this embodiment, the evaporative crystallization process includes the steps of:
and filtering to obtain industrial new water and concentrated water containing chloride ions. The filtration treatment refers to a process of purifying wastewater by a special device, which may be a nanofiltration membrane element, which refers to a functional semi-permeable membrane that allows the permeation of solvent molecules or certain low molecular weight solutes or low valence ions. Thus, the wastewater is subjected to nanofiltration membrane separation treatment to obtain industrial new water and concentrated water;
the concentrated water is evaporated for obtaining industrial salt. The evaporation treatment refers to a method for removing water by boiling concentrated water so as to concentrate radioactive pollutants in wastewater, and the evaporation treatment can be carried out by means of an evaporation crystallization device to carry out sodium chloride evaporation crystallization.
Notably, the filtering process includes the following steps;
and (3) primary nanofiltration treatment: part of chloride ions pass through the first-stage nanofiltration water to intercept sulfate ions to form first-stage concentrated water. Specifically, during the first-stage nanofiltration treatment, divalent sulfate radicals are intercepted to the concentrated water side by utilizing the selective permeability of the nanofiltration membrane element, and monovalent chloride ions can enter the water producing side, namely the first-stage nanofiltration water producing pool, through the nanofiltration membrane. After the first-stage nanofiltration treatment, concentrated water is collected in a middle water tank and can be diluted by evaporating condensed water;
and (3) secondary nanofiltration treatment: so that partial chloride ions in the first-stage concentrated water form second-stage nanofiltration water, and sulfate ions are intercepted to form second-stage concentrated water. Specifically, the concentrated water after the primary nanofiltration treatment and dilution enters the secondary nanofiltration for secondary treatment, so that the chloride ion concentration of the secondary nanofiltration concentrated water is ensured to be less than 2000mg/L, and the water quality requirement of flue gas cooling and spraying is met;
reverse osmosis treatment; and part of the solution passes through the industrial fresh water to intercept chloride ions to form tertiary concentrated water. Specifically, the produced water after the secondary nanofiltration treatment needs to be concentrated by the reverse osmosis treatment system, wherein NaCl is enriched in the concentrated solution. Therefore, the produced water after the reverse osmosis treatment meets the water quality recycling of industrial new water.
Notably, the industrial salt is obtained by evaporating the concentrated water after the primary nanofiltration water and the tertiary concentrated water are mixed. Specifically, the concentrated water after reverse osmosis treatment enters the first-stage nanofiltration water producing pond, is mixed with the water produced after the first-stage nanofiltration treatment, and sequentially enters the evaporation crystallization device, and is subjected to concentrated water evaporation treatment to obtain industrial salt.
The filtering process further includes: and adding evaporation condensate water to dilute the primary concentrated water, and performing secondary nanofiltration treatment, wherein the concentrated water is collected in an intermediate water tank after the primary nanofiltration treatment, and can be discharged into the secondary nanofiltration treatment after the evaporation condensate water is diluted.
And the mother liquor generated in the evaporation treatment is refluxed and subjected to the chemical pretreatment, and the chloride ion concentration of the secondary nanofiltration water after the secondary nanofiltration treatment meets the water quality requirement of flue gas cooling spraying, namely the chloride ion concentration of the secondary nanofiltration concentrated water is less than 2000mg/L. The concentrated water enters a flue gas spraying system, and the water is condensed into a slurry circulating system of the desulfurizing tower; the evaporated crystal (sodium sulfate and the like) enters an electric dust collector along with dust and is discharged along with the dust, and then enters the subsequent desulfurization wastewater treatment to produce gypsum.
In this embodiment, the chemical pretreatment includes the following steps:
and (3) defluorination treatment by electric flocculation, which is used for removing fluorine ions in the wastewater. Specifically, the electric flocculation defluorination treatment can use an electric flocculation device to lift the wastewater into the electric flocculation device, a soluble anode (aluminum plate) is dissolved to generate a large amount of aluminum ions under the action of current, the aluminum ions are hydrolyzed and polymerized to form a series of polynuclear hydroxyl complexes and hydroxides, the products have strong adsorption capacity, the products have the actions of condensation, adsorption and the like with fluorine ions in the wastewater to form suspended matters, and the fluorine ions in the wastewater are removed through solid-liquid separation;
and (3) calcium removal treatment for separating calcium ions in the wastewater. Specifically, wastewater subjected to defluorination treatment and defluorination enters a calcium removal treatment, namely a calcium removal reaction unit, and in the reaction unit, alkali, sodium carbonate, polymeric ferric sulfate and other medicaments are added, so that under the condition that the pH is regulated to be more than 10, calcium carbonate, mercury hydroxide and other precipitates are generated, and solid-liquid separation is carried out through tubular microfiltration;
and the tube-type microfiltration treatment is used for removing hardness after the calcium removal treatment. Specifically, the hardness in the wastewater is removed by the tubular microfiltration treatment.
It is noted that the electric flocculation defluorination treatment and the tubular microfiltration treatment both produce sludge, and the sludge is concentrated and dehydrated and then sintered to form a sintered mixture, wherein the sintered mixture is formed by mixing and then granulating. The mixture is sintered by mixing and subsequent granulation.
Notably, the chemical pretreatment further comprises the steps of:
the wastewater after the tubular microfiltration treatment is subjected to hard removal treatment and mercury removal treatment in sequence;
the hardness removal treatment is used for removing residual hardness in the wastewater. Specifically, the waste water after the hard is filtered by the tubular micro-filter is lifted by a water pump to enter a hard-removing chelating resin tank, and the residual hardness in the waste water is removed by the depth of the resin;
the mercury removal treatment is used for removing mercury in the wastewater. Specifically, the waste water after the hard removal treatment is lifted by a water pump to enter a mercury removal resin tank, and total mercury in the waste water is removed by utilizing the depth of resin, and the produced water of the mercury removal resin tank is collected in a resin produced water tank. The method is used for ensuring the stable and efficient operation of the subsequent system and ensuring that the water produced by the system meets the requirements. And refluxing the regenerated liquid generated by the hard chelating resin tank and the mercury removing resin tank, and performing chemical pretreatment to perform cyclic treatment.
In this embodiment, the deamination process comprises the steps of:
and adding sulfuric acid into the wastewater after the chemical pretreatment. Specifically, the produced water after the chemical pretreatment, namely the produced water after the mercury removal treatment, is lifted by a water pump to enter a deamination membrane system, and sulfuric acid is added into the deamination membrane system;
the sulfuric acid is used to remove ammonia from the wastewater and produce ammonium sulfate. Specifically, free NH3 is absorbed with the added sulfuric acid, yielding by-product ammonium sulfate. The method comprises the steps of carrying out a first treatment on the surface of the
And regulating the pH value of the residual wastewater to be neutral. Specifically, ammonia nitrogen in the wastewater is reduced to below 5ppm by the deamination membrane system, produced water is collected in a deamination membrane produced water tank, and the produced water is lifted into the primary nanofiltration device after PH is adjusted to be neutral.
In an alternative embodiment, the chemical pretreatment is preceded by a plant pretreatment for reducing the COD index of the wastewater. Specifically, after the wastewater outside the workshop is pretreated in the workshop, the effluent is conveyed to an aeration adjusting tank, and is mixed with sludge dewatering filtrate, MVR evaporation mother liquor, resin regeneration liquid and membrane system chemical cleaning liquid, and the effluent is homogenized and the COD index of the wastewater is reduced by oxidizing the reducing inorganic matters in the raw water through aeration while the average amount is homogenized, so that the prior art is omitted.
Notably, in the chemical pretreatment, the regenerated liquid of the hard resin and the mercury resin is returned to the aeration adjusting tank for circulation treatment.
It is noted that in the evaporation crystallization treatment, a very small amount of evaporation mother liquor generated in the evaporation process flows back into the aeration adjusting tank for further treatment.
The present application is described in further detail below by way of examples to enable those skilled in the art to practice the same by reference to the specification.
Examples:
drainage 5m of sintering acid production wastewater workshop 3 And/h, considering 120% allowance, designing a treatment scale of 6m 3 And/h, sintering acid-making wastewater (6 m) 3 /h), regeneration liquid (0.1 m) for removing hard resin 3 /h), evaporation mother liquor (0.1 m 3 /h), membrane system chemical cleaning solution (0.1 m 3 (h) homogenizing in a conditioning tank with a throughput of 6.3m 3 And/h, the main water quality after adjustment is as follows: 60000mg/L of chloride, 200mg/L of ammonia nitrogen, 550mg/L of fluoride, 2000mg/L of sulfate radical and 0.05mg/L of total mercury, and is lifted into a subsequent pretreatment unit;
after the electric flocculation defluorination, tubular micro-filtration hard removal, hard removal resin removal and mercury removal resin process treatment, the fluoride ions in the wastewater are less than 20mg/L, the total hardness is less than 10mg/L, the total mercury is less than 0.01mg/L, sludge generated by an electric flocculation unit and a calcium removal reaction unit is discharged into a sludge concentration tank, and resin regeneration liquid is periodically discharged into an aeration regulating tank for internal circulation treatment;
the sludge in the sludge concentration tank is subjected to periodical filter pressing and dehydration treatment, supernatant is returned to the aeration regulating tank, and filter cakes are sent to the main process for sintering and stirring;
the pretreated wastewater is lifted to enter the deamination membrane system, free ammonia nitrogen is absorbed by sulfuric acid in the process section, by-product ammonium sulfate is produced, ammonia nitrogen in the wastewater is reduced to less than 5mg/L through the deamination membrane system, and produced water is lifted to enter the membrane concentration/separation system;
the treatment capacity of wastewater after deamination treatment is 6.3m 3 And (3) lifting to enter a first stage, separating Cl & lt- & gt and SO & lt 42 & gt in the wastewater, and intercepting divalent ions SO & lt 42 & gt and part of Cl & lt- & gt in the wastewater on the concentrated water side, wherein the produced water is mainly Cl & lt- & gt, SO that the purity of a solution entering an evaporation crystallization system is improved, and the quality of sodium chloride industrial salt produced by evaporation crystallization is ensured;
the first-stage nanofiltration concentrated water (0.2 m 3 Collecting in middle water pond, diluting with evaporated condensate water, performing secondary nanofiltration, and treating again to ensure chloride ion concentration of secondary nanofiltration concentrated water<2000mg/L, which meets the water quality requirement of flue gas cooling spray, the secondary nanofiltration produced water mainly takes low concentration Cl & lt- & gt as the main component, and is lifted to enter a reverse osmosis system for re-concentration, the produced water is industrial new water, and the concentrated water is discharged into a primary nanofiltration produced water tank and is mixed to enter an evaporation crystallization unit;
the project designs the processing capacity of 6m through the processing technology 3 And/h, finally obtaining the industrial productFresh water 5.6m 3 Per hour, industrial salt to 0.5 t/hour, 6 percent ammonium sulfate solution to 0.07 t/hour and flue gas cooling spray water to 0.3m 3 And/h and a small amount of sludge, thereby realizing zero discharge of sintering acid making wastewater.
The conventional treatment of the conventional sintering acid-making wastewater is carried out, and the wastewater is discharged to a subsequent process for further treatment after being pretreated in a workshop, and the wastewater is high in impact on the subsequent process, equipment material corrosion and effluent quality due to large fluctuation of water quality, high salt content, complex components, poor biodegradability and difficult degradation; and then flushing slag in a blast furnace and making steel and sealing slag. Because the indexes of salt content, ammonia nitrogen and the like of the wastewater are high, the slag treatment area has peculiar smell and is not friendly to the environment, and meanwhile, the gas generated by the disintegrating slag of the wastewater has serious corrosion to plants and equipment.
In summary, the present application provides a method for zero emission treatment of sintering acid-making wastewater, which includes chemical pretreatment, deamination treatment and evaporative crystallization treatment; the chemical pretreatment comprises electric flocculation defluorination device treatment and tubular microfiltration treatment; the deamination process has a deamination device comprising a deamination membrane system; the evaporation crystallization treatment comprises reverse osmosis treatment, primary nanofiltration treatment, secondary nanofiltration treatment, and two sets of corresponding membrane cleaning systems and reverse osmosis systems. After the treatment process, the zero emission of the sintering acid making wastewater is realized, the produced reuse water meets the water quality requirement of industrial new water, is taken as process supplementing water, and further obtains products such as industrial salt products, ammonium sulfate and the like, and a small amount of residual concentrated water is taken as flue gas cooling water for spraying, so that the whole treatment process does not produce mixed salt, can be recycled, and simultaneously does not additionally produce solid waste. The application can recycle the resources in the wastewater, such as sulfuric acid, industrial salt, ammonium sulfate and other products, has high economic value, can effectively remove pollutants in the wastewater by adopting various treatment processes in the treatment engineering, ensures the stability and reliability of the treatment process, and generates high-quality accessory products, such as industrial salt, ammonium sulfate and other products in the treatment process, thereby having high market competitiveness. In a word, the application has high environmental protection value and economic benefit, can effectively reduce pollutant emission, recycle resources and reduce environmental pollution and economic cost.
The foregoing description is only illustrative of the preferred embodiments of the present application and is not intended to limit the scope of the present application, and any changes and modifications made by those skilled in the art in light of the above disclosure will fall within the scope of the present application.
Claims (10)
1. A method for zero emission treatment of sintering acid making wastewater is characterized by comprising the following steps: the method comprises the following steps:
chemical pretreatment for pretreating the wastewater to reduce fluorine ions, calcium ions and heavy metal ions in the sintering acid-making wastewater;
deamination treatment for removing ammonia nitrogen in wastewater;
and (3) performing evaporative crystallization treatment, namely performing membrane separation treatment on the wastewater to obtain industrial new water and concentrated water, and performing evaporative crystallization treatment on the concentrated water to obtain industrial salt.
2. The method for zero emission treatment of sintering acid-making wastewater according to claim 1, wherein the method comprises the following steps: the evaporative crystallization treatment comprises the following steps:
filtering to obtain industrial new water and concentrated water containing chloride ions;
the concentrated water is evaporated for obtaining industrial salt.
3. The method for zero emission treatment of sintering acid-making wastewater according to claim 2, wherein: the filtering process includes the following steps;
and (3) primary nanofiltration treatment: part of chloride ions pass through the first-stage nanofiltration water to intercept sulfate ions to form first-stage concentrated water;
and (3) secondary nanofiltration treatment: so that part of chloride ions in the first-stage concentrated water pass through the second-stage nanofiltration water to intercept sulfate ions to form the second-stage concentrated water;
reverse osmosis treatment; and part of the solution passes through the industrial fresh water to intercept chloride ions to form tertiary concentrated water.
4. A method for the zero release treatment of sintering acid production wastewater according to claim 3, characterized in that: and mixing the first-stage nanofiltration water with the third-stage concentrated water, and then performing concentrated water evaporation treatment to obtain industrial salt.
5. A method for the zero release treatment of sintering acid production wastewater according to claim 3, characterized in that: the filtering process further includes: and adding the evaporated condensate water to the first-stage concentrated water for dilution, and then carrying out second-stage nanofiltration treatment.
6. The method for zero emission treatment of sintering acid-making wastewater according to claim 2, wherein: and the mother liquor generated in the evaporation treatment is refluxed and subjected to chemical pretreatment, and the chloride ion concentration of the secondary nanofiltration water after the secondary nanofiltration treatment meets the water quality requirement of flue gas cooling and spraying.
7. The method for zero emission treatment of sintering acid-making wastewater according to claim 1, wherein the method comprises the following steps: the chemical pretreatment comprises the following steps:
the electric flocculation defluorination treatment is used for removing fluorine ions in the wastewater;
calcium removal treatment for separating calcium ions in the wastewater;
and the tube-type microfiltration treatment is used for removing hardness after the calcium removal treatment.
8. The method for zero emission treatment of sintering acid-making wastewater according to claim 7, wherein: and sludge is generated after the electric flocculation defluorination treatment and the tubular microfiltration treatment, and the sludge is sintered and mixed after being concentrated and dehydrated.
9. The method for zero emission treatment of sintering acid-making wastewater according to claim 7, wherein: the chemical pretreatment further comprises the following steps:
the wastewater after the tubular microfiltration treatment is subjected to hard removal treatment and mercury removal treatment in sequence;
the hardness removal treatment is used for removing residual hardness in the wastewater;
the mercury removal treatment is used for removing mercury in the wastewater.
10. The method for zero emission treatment of sintering acid-making wastewater according to claim 1, wherein the method comprises the following steps: the deamination treatment comprises the following steps:
adding sulfuric acid into the wastewater subjected to the chemical pretreatment;
the sulfuric acid is used for removing ammonia in the wastewater and generating ammonium sulfate;
and regulating the pH value of the residual wastewater to be neutral.
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