CN117000216A - Chelating agent, industrial treatment system and treatment method for desulfurization wastewater of coal-fired power plant - Google Patents
Chelating agent, industrial treatment system and treatment method for desulfurization wastewater of coal-fired power plant Download PDFInfo
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- CN117000216A CN117000216A CN202311283139.7A CN202311283139A CN117000216A CN 117000216 A CN117000216 A CN 117000216A CN 202311283139 A CN202311283139 A CN 202311283139A CN 117000216 A CN117000216 A CN 117000216A
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- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 394
- 230000023556 desulfurization Effects 0.000 title claims abstract description 389
- 239000002351 wastewater Substances 0.000 title claims abstract description 203
- 238000011282 treatment Methods 0.000 title claims abstract description 127
- 239000002738 chelating agent Substances 0.000 title claims abstract description 123
- 238000000034 method Methods 0.000 title claims abstract description 48
- 239000010802 sludge Substances 0.000 claims abstract description 202
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 173
- 150000002500 ions Chemical class 0.000 claims abstract description 144
- 238000006243 chemical reaction Methods 0.000 claims abstract description 98
- 238000001914 filtration Methods 0.000 claims abstract description 62
- 150000003839 salts Chemical class 0.000 claims abstract description 57
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 46
- 238000011084 recovery Methods 0.000 claims abstract description 42
- 239000007788 liquid Substances 0.000 claims abstract description 41
- 238000002360 preparation method Methods 0.000 claims abstract description 39
- 238000000926 separation method Methods 0.000 claims abstract description 39
- 239000002002 slurry Substances 0.000 claims abstract description 39
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 38
- 239000012266 salt solution Substances 0.000 claims abstract description 37
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 33
- DAFOCGYVTAOKAJ-UHFFFAOYSA-N phenibut Chemical compound OC(=O)CC(CN)C1=CC=CC=C1 DAFOCGYVTAOKAJ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000001704 evaporation Methods 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 21
- 239000002244 precipitate Substances 0.000 claims abstract description 19
- 150000002009 diols Chemical class 0.000 claims abstract description 10
- 238000001514 detection method Methods 0.000 claims description 113
- 239000002994 raw material Substances 0.000 claims description 101
- 239000003546 flue gas Substances 0.000 claims description 84
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 82
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 45
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 41
- 238000001816 cooling Methods 0.000 claims description 38
- 235000011089 carbon dioxide Nutrition 0.000 claims description 33
- 239000012528 membrane Substances 0.000 claims description 33
- 239000000126 substance Substances 0.000 claims description 29
- 239000002893 slag Substances 0.000 claims description 26
- MTVWFVDWRVYDOR-UHFFFAOYSA-N 3,4-Dihydroxyphenylglycol Chemical compound OCC(O)C1=CC=C(O)C(O)=C1 MTVWFVDWRVYDOR-UHFFFAOYSA-N 0.000 claims description 25
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical class [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 24
- 239000012024 dehydrating agents Substances 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 21
- 230000009920 chelation Effects 0.000 claims description 20
- 230000018044 dehydration Effects 0.000 claims description 19
- 238000006297 dehydration reaction Methods 0.000 claims description 19
- 239000000376 reactant Substances 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 18
- 238000003860 storage Methods 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 15
- GPAPPPVRLPGFEQ-UHFFFAOYSA-N 4,4'-dichlorodiphenyl sulfone Chemical compound C1=CC(Cl)=CC=C1S(=O)(=O)C1=CC=C(Cl)C=C1 GPAPPPVRLPGFEQ-UHFFFAOYSA-N 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 239000012716 precipitator Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 10
- 238000001556 precipitation Methods 0.000 claims description 10
- 239000007790 solid phase Substances 0.000 claims description 10
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 229910001220 stainless steel Inorganic materials 0.000 claims description 9
- 239000010935 stainless steel Substances 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 239000000835 fiber Substances 0.000 claims description 7
- 238000009472 formulation Methods 0.000 claims description 7
- 238000000108 ultra-filtration Methods 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 4
- 239000004071 soot Substances 0.000 claims description 4
- 150000003568 thioethers Chemical class 0.000 claims description 4
- 239000003570 air Substances 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 238000004065 wastewater treatment Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 description 19
- 238000001179 sorption measurement Methods 0.000 description 19
- 208000005156 Dehydration Diseases 0.000 description 18
- 230000008020 evaporation Effects 0.000 description 13
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 10
- 229910052602 gypsum Inorganic materials 0.000 description 10
- 239000010440 gypsum Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 238000004062 sedimentation Methods 0.000 description 8
- 239000012267 brine Substances 0.000 description 7
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 7
- 239000000920 calcium hydroxide Substances 0.000 description 7
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 7
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 6
- 238000012544 monitoring process Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 5
- 235000019341 magnesium sulphate Nutrition 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- 238000012994 industrial processing Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920002401 polyacrylamide Polymers 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- 206010063385 Intellectualisation Diseases 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000011217 control strategy Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- XSYRYMGYPBGOPS-UHFFFAOYSA-N 4-amino-3-phenylbutanoic acid;hydrochloride Chemical compound [Cl-].OC(=O)CC(C[NH3+])C1=CC=CC=C1 XSYRYMGYPBGOPS-UHFFFAOYSA-N 0.000 description 2
- -1 Cr 2+ Chemical class 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005352 clarification Methods 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
- 230000003009 desulfurizing effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- 238000005496 tempering Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000011269 treatment regimen Methods 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
-
- 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
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/14—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents
- C02F11/143—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents using inorganic substances
- C02F11/145—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents using inorganic substances using calcium compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/14—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents
- C02F11/147—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents using organic substances
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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
- C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
-
- 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
-
- 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
- C02F1/66—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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- 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
Abstract
The invention provides a chelating agent, an industrial treatment system and a treatment method for desulfurization wastewater of a coal-fired power plant, and belongs to the technical field of desulfurization wastewater treatment, wherein the chelating agent comprises the following components: 4-amino-3-phenylbutyrate, DL-3, 4-dihydroxyphenyl diol, 4' -dichlorodiphenyl sulfone and nano SiO 2 Modified polyacrylic resin. The system comprises: the device comprises a chelating agent preparation unit, a desulfurization wastewater reaction unit, a filtering unit, a neutralization reaction unit, a solid-liquid separation unit, a desulfurization sludge treatment unit and a salt solution recovery unit; the method comprises the following steps: removing heavy metal ions in the desulfurization wastewater by using a chelating agent; filtering the flocculent precipitate; adjusting the pH value of the desulfurization wastewater; separating salt-containing slurry from desulfurization sludge; dehydrating the desulfurized sludge; concentrating, evaporating and drying the salt-containing slurry. By the method provided by the invention, the removal rate of each heavy metal ion in the desulfurization sludge is close to 100%, and the moisture content in the desulfurization sludge is lower than 50%.
Description
Technical Field
The invention relates to the technical field of desulfurization wastewater treatment, in particular to a heavy metal ion chelating agent, an industrial treatment system of desulfurization wastewater of a coal-fired power plant and an industrial treatment method of desulfurization wastewater of the coal-fired power plant.
Background
In the operation process of the power plant, the main wastewater discharged outwards comprises circulating sewage, refined strong brine and desulfurization wastewater. Among them, desulfurization wastewater is the most common wastewater. The desulfurization wastewater has acidic water quality, high salt content, high hardness, high content of suspended solids (suspended solids), large water quality change and the like, and has stronger corrosiveness. Because the components of the desulfurization waste water are complex, the untreated desulfurization waste water cannot be directly discharged, and the desulfurization waste water can be discharged only after being treated by a desulfurization waste water treatment system to reach the discharge standard. Therefore, the treatment of desulfurization wastewater is a key point for realizing zero emission of wastewater of coal-fired power plants.
In the prior art, the most commonly used desulfurization wastewater treatment technology is limestone-gypsum wet desulfurization technology, and the technology mainly adopts limestone and gypsum for desulfurization, has the characteristics of high desulfurization efficiency, capability of adapting to the large fluctuation of sulfur content change and the like, and realizes the maximum utilization rate of the desulfurizing agent. However, limestone-gypsum wet desulfurization techniques can result in increased desulfurization byproducts, such as desulfurization sludge. This is because the quality of desulfurization wastewater is acidic, the content of solid suspended matters is high, and suspended matters particles are fine, wherein the main component is byproducts of desulfurization such as CaSO 3 、CaSO 4 And the like, dust, soluble nitrates, fluorides and chlorides, and heavy metal elements such as Cr, ni, cu, zn, as, cd, pb, hg. After the materials are subjected to conventional single-stage treatment, most pollutants in the materials are all enriched in desulfurization sludge although the water quality of the desulfurization wastewater reaches DLT997-2020 'limestone-gypsum wet desulfurization wastewater Water quality control index of coal-fired power plants'. Analysis of the main components in the desulfurization sludge revealed that the desulfurization sludge contained a large amount of CaSO 4 ·2H 2 O gypsum component, and also contains Cr, ni, cu, zn, as, cd, pb, hg heavy metal element, caSO 4 ·2H 2 The O gypsum component can increase the viscosity of the desulfurization sludge, has poor dehydration performance and leads to high water content of the desulfurization sludge. This is because the gypsum component in the desulfurization sludge will crystallize a part of free water inside the gypsum when crystallizing, resulting in a high water content of the desulfurization sludge; meanwhile, chloride ions and calcium ions in the desulfurization wastewater can form calcium chloride, the formed calcium chloride exists among gypsum grains, and the calcium chloride has super-high water absorbability, so that the water content of desulfurization sludge is further increased. Therefore, the desulfurization wastewater is treated, and the desulfurization sludge is also treated, so that the harm of the desulfurization wastewater and byproducts thereof to the environment is reduced.
However, it is known from a review of the prior art that the existing desulfurization wastewater treatment system and treatment method rarely performs the next treatment on the desulfurization sludge obtained later. Although some coal-fired power plants can independently set up a set of treatment flow for the desulfurization sludge, the treatment effect is not good, and the treatment mode for heavy metal elements in the desulfurization sludge is limited. For example, a system for desulfurizing waste water by coupling low-temperature flue gas with dry slag waste heat is proposed in China patent document with publication No. CN113277585A, wherein the system is characterized in that low-temperature flue gas is introduced as a heat source, concentrated slurry is obtained after concentration and demisting, the concentrated slurry is subjected to tempering and neutralization and then is introduced into a quality-regulating clarification tank for treatment, sludge with solid-liquid separation and salt-containing slurry are obtained, wherein the sludge is subjected to centralized treatment through a sludge collector at the bottom of the tempering clarification tank, the salt-containing slurry is subjected to evaporation and drying treatment through a salt-containing slurry discharge device to form salt-containing dust, and the salt-containing dust enters dry slag for recycling. The desulfurization sludge is only collected and is not subjected to the specific treatment in the next step. Although this method also has a separate treatment of the subsequent desulfurization sludge, the treatment effect is not good.
The Chinese patent literature with publication number CN115818680A and publication number 2023 and 3 and 21 proposes a treatment method of magnesium desulfurization sludge, which comprises pretreating magnesium desulfurization sludge to obtain slurry, and mixing the slurry with air to obtain a gas-liquid mixture; mixing the gas-liquid mixture with an oxidant, and reacting under the action of a catalyst to obtain a reaction liquid; clarifying and filtering the reaction solution to obtain a magnesium sulfate solution; evaporating, concentrating, cooling and crystallizing the magnesium sulfate solution to obtain magnesium sulfate crystals. Although the method can efficiently obtain the magnesium sulfate with higher conversion rate, reduce the energy consumption of oxidation concentration and the cost for producing the magnesium sulfate, the method obviously does not specifically treat other components in the desulfurization sludge, such as gypsum and heavy metal elements, has poor treatment effect, and does not obviously reduce the harm of desulfurization wastewater and byproducts thereof to the environment.
The Chinese patent literature with publication number CN109320043A and publication number 2019, 2 and 12, proposes a method for stabilizing heavy metals in desulfurization sludge by using a microwave coupling stabilizer. However, the method only aims at treating heavy metal elements in the desulfurization sludge, particularly Hg, and a microwave-coupled NaS stabilizer is combined with Hg of the desulfurization sludge to form a indissolvable, low-toxicity and very stable compound HgS, so that the leaching toxicity of Hg is reduced. In addition, the method does not solve the problems of high viscosity, poor dehydration performance and high water content of the desulfurization sludge.
It is thus seen that there is a need for an industrial treatment method and system for desulfurization wastewater from coal-fired power plants that achieves zero emission of desulfurization wastewater and its by-products, desulfurization sludge.
Disclosure of Invention
Aiming at the technical problems that the prior art of the prior desulfurization wastewater treatment process and the subsequent desulfurization wastewater byproduct-desulfurization sludge treatment process are separately carried out, the industrial continuous treatment of desulfurization wastewater of a coal-fired power plant and the byproduct-desulfurization sludge thereof cannot be realized, and the treatment mode of heavy metal elements in the desulfurization sludge has certain limitation, the invention provides a chelating agent, an industrial treatment system and a treatment method for desulfurization wastewater of the coal-fired power plant, which can greatly improve the removal rate of heavy metal ions.
To achieve the above object, a first aspect of the present invention provides an industrial treatment system for desulfurization wastewater of a coal-fired power plant, the industrial treatment system comprising: the device comprises a chelating agent preparation unit, a desulfurization wastewater reaction unit, a filtering unit, a neutralization reaction unit, a solid-liquid separation unit, a desulfurization sludge treatment unit and a salt solution recovery unit; wherein the chelating agent preparation unit is used for preparing 4-amino-3-phenylbutyrate, DL-3, 4-dihydroxyphenyl glycol, 4' -dichlorodiphenyl sulfone and nano SiO 2 The modified polyacrylic resin is prepared into a heavy metal ion chelating agent; the inlet of the desulfurization wastewater reaction unit is communicated with the outlet of the chelating agent preparation unit and is used for mixing a heavy metal ion chelating agent with desulfurization wastewater and carrying out chelating reaction; the inlet of the filtering unit is communicated with the outlet of the desulfurization wastewater reaction unit and is used for filtering flocculent precipitate in the desulfurization wastewater subjected to the chelation reaction to obtain desulfurization wastewater after heavy metal ions are removed; the inlet of the neutralization reaction unit is communicated with the outlet of the filtering unit and is used for mixing alkaline substances with the desulfurization wastewater after heavy metal ions are removed and carrying out neutralization reaction to obtain the desulfurization wastewater after the pH value is regulated; the inlet of the solid-liquid separation unit is communicated with the outlet of the neutralization reaction unit and is used for separating salt-containing slurry in the desulfurization wastewater with the pH value adjustedCarrying out solid-liquid separation on the liquid and the desulfurization sludge; the inlet of the desulfurization sludge treatment unit is communicated with the sludge outlet of the solid-liquid separation unit and is used for removing the moisture content in the desulfurization sludge; and the inlet of the salt solution recovery unit is communicated with the salt solution outlet of the solid-liquid separation unit and is used for concentrating, evaporating and drying the salt-containing slurry to obtain salt-containing solid powder.
In one exemplary embodiment of the present invention, the chelating agent formulation unit may include: a first feedstock tank, a second feedstock tank, a third feedstock tank, a fourth feedstock tank, and a chelating agent formulation tank; the first raw material tank, the second raw material tank, the third raw material tank and the fourth raw material tank are respectively communicated with the inlet of the chelating agent preparation tank; the first raw material tank is used for storing 4-amino-3-phenylbutyrate; the second raw material tank is used for storing DL-3, 4-dihydroxyphenyl glycol; the third raw material tank is used for storing 4,4' -dichloro diphenyl sulfone; the fourth raw material tank is used for storing nano SiO 2 Modified polyacrylic resin; the chelating agent preparation tank is used for preparing 4-amino-3-phenylbutyrate, DL-3, 4-dihydroxyphenyl glycol, 4' -dichlorodiphenyl sulfone and nano SiO 2 The modified polyacrylic resin is prepared into a heavy metal ion chelating agent according to a first preset mass ratio; wherein the 4-amino-3-phenylbutyrate, the DL-3, 4-dihydroxyphenyl diol, the 4,4' -dichlorodiphenyl sulfone and the nano SiO 2 The first preset mass ratio of the modified polyacrylic resin is (1.2-3.5) to (2.1-3.8): (1.4 to 2.5): (5.0 to 9.5).
In an exemplary embodiment of the present invention, the industrial processing system may further include: a flue gas channel and a flue gas cooling unit; the flue gas channel is used for conveying flue gas discharged by a coal-fired power plant induced draft fan, and the flue gas comprises: carbon dioxide, sulfides, nitrogen oxides, air, soot, and ammonia; an inlet of the flue gas cooling unit is communicated with the flue gas channel and is used for cooling the flue gas to 45-50 ℃; the outlet of the flue gas cooling unit is communicated with the inlet of the desulfurization wastewater reaction unit and is used for introducing cooled flue gas into the desulfurization wastewater.
In an exemplary embodiment of the present invention, the flue gas cooling unit may include: a dry ice storage tank and a dry ice ejector; the dry ice ejector is arranged on the dry ice storage box, the inlet of the dry ice storage box is communicated with the flue gas channel, and the outlet of the dry ice storage box is communicated with the inlet of the desulfurization wastewater reaction unit.
In one exemplary embodiment of the present invention, the solid-liquid separation unit may include: a centrifugal precipitator, a filtering membrane and a water pump; the filtering membrane is transversely arranged in the centrifugal precipitation machine and comprises a stainless steel filtering screen, a fiber filtering membrane and a micron-sized ultrafiltration membrane which are arranged in sequence from bottom to top; the inlet of the water pump is communicated with the salt solution outlet of the centrifugal precipitation machine, and the outlet of the water pump is communicated with the inlet of the salt solution recovery unit.
In an exemplary embodiment of the present invention, the desulfurization sludge treatment unit may include: a fifth raw material tank, a sixth raw material tank, a desulfurization sludge treatment tank and a desulfurization sludge dehydration tank; the fifth raw material tank is used for storing modified calcium silicate slag; the sixth raw material tank is used for storing a dehydrating agent; the fifth raw material tank and the sixth raw material tank are respectively communicated with an inlet of the desulfurization sludge treatment tank, and the desulfurization sludge treatment tank is used for fully mixing the modified calcium silicate slag, the dehydrating agent and the desulfurization sludge; the desulfurization sludge dewatering tank is communicated with the outlet of the desulfurization sludge treatment tank and is used for mechanically dewatering the mixed desulfurization sludge.
In an exemplary embodiment of the present invention, the industrial processing system may further include: an online detection unit, the online detection unit may include: the device comprises a first detection module, a second detection module, a third detection module, a fourth detection module, a fifth detection module and a sixth detection module; the first detection module is used for detecting the air pressure and the temperature in the desulfurization wastewater reaction unit; the second detection module is used for detecting the concentration of each reactant in the chelating agent preparation unit; the third detection module is used for detecting the pH value in the neutralization reaction unit; the fourth detection module is used for detecting the salt concentration in the solid-liquid separation unit; the fifth detection module is used for detecting the water content of the desulfurization sludge in the desulfurization sludge treatment unit; the sixth detection module is used for detecting the water content of the salt solution in the salt solution recovery unit.
In an exemplary embodiment of the present invention, the industrial processing system may further include: a control unit; the control unit is used for receiving the multiple detection data output by the online detection unit and outputting corresponding control decisions.
In a second aspect, the present invention provides a heavy metal ion chelating agent comprising: 4-amino-3-phenylbutyrate, DL-3, 4-dihydroxyphenyl diol, 4' -dichlorodiphenyl sulfone and nano SiO 2 Modified polyacrylic resin; wherein the 4-amino-3-phenylbutyrate, the DL-3, 4-dihydroxyphenyl diol, the 4,4' -dichlorodiphenyl sulfone and the nano SiO 2 The first preset mass ratio of the modified polyacrylic resin is (1.2-3.5) to (2.1-3.8): (1.4 to 2.5): (5.0 to 9.5).
The invention provides an industrial treatment method of desulfurization wastewater of a coal-fired power plant, which is realized by the industrial treatment system and comprises the following steps: adding a heavy metal ion chelating agent into the desulfurization wastewater, and carrying out chelation reaction on the heavy metal ion chelating agent and heavy metal ions in the desulfurization wastewater by continuous stirring to generate desulfurization wastewater with flocculent precipitate; filtering flocculent precipitate in the desulfurization wastewater after the chelation reaction to obtain desulfurization wastewater after heavy metal ions are removed; adding alkaline substances into the desulfurization wastewater from which heavy metal ions are removed, and carrying out neutralization reaction on the alkaline substances and the desulfurization wastewater by continuous stirring to obtain desulfurization wastewater with the pH value of 7-13; carrying out solid-liquid separation on the desulfurization wastewater with the pH value of 7-13 to respectively obtain salt-containing slurry and desulfurization sludge; removing the moisture content in the desulfurization sludge; concentrating, evaporating and drying the salt-containing slurry to obtain salt-containing solid powder.
In another exemplary embodiment of the present invention, the removing the moisture content in the desulfurization sludge may include: firstly, sequentially adding modified calcium silicate slag and a dehydrating agent into the desulfurization sludge, continuously stirring, and then mechanically dehydrating the mixed desulfurization sludge to obtain the desulfurization sludge with the moisture content lower than 50%.
In another exemplary embodiment of the present invention, the second predetermined mass ratio of the solid phase material in the modified calcium silicate slag and the desulphurized sludge may be (0.1 to 0.3) to (1 to 1.2); the third predetermined mass ratio of the dehydrating agent to the solid phase substance in the desulfurization sludge can be (0.05-0.1) to (1-1.2).
In another exemplary embodiment of the present invention, flue gas at 45 ℃ to 50 ℃ may be introduced into the desulfurization wastewater during the chelation reaction of the heavy metal ion chelating agent and the heavy metal ions in the desulfurization wastewater.
Through the technical scheme provided by the invention, the invention has at least the following technical effects:
(1) According to the invention, the novel heavy metal ion chelating agent is prepared, so that the removal rate of heavy metal ions is greatly improved (the removal rate of each heavy metal ion is close to 100%), and the heavy metal ion chelating agent has higher adsorption capacity for heavy metal ions and can be used for adsorbing heavy metal ions more strongly;
(2) The invention takes the low-temperature flue gas after cooling treatment as the catalyst of the chelation reaction, thereby not only accelerating the chelation reaction rate and assisting in improving the heavy metal ion adsorption effect, but also realizing the recycling of the flue gas of the coal-fired power plant;
(3) According to the invention, by designing the solid-liquid separator in the structural form of the centrifugal precipitator, the filtering membrane and the high-power water pump, not only is the efficient separation of the salt-containing slurry and the desulfurized sludge realized, but also the water content in the desulfurized sludge after final dehydration is reduced in an auxiliary manner;
(4) According to the invention, the modified calcium silicate slag and the dehydrating agent are physically combined with the desulfurization sludge, so that the overall dehydration performance of the desulfurization sludge is improved, and the moisture content of the desulfurization sludge is reduced to below 50% under the synergistic effect of mechanical dehydration, so that the viscosity of the desulfurization sludge is reduced;
(5) According to the invention, the control unit and the online detection unit are arranged, so that the desulfurization wastewater treatment and intelligent control of the coal-fired power plant are combined, and the industrial rapid and accurate treatment of the desulfurization wastewater is realized;
(6) The invention can realize zero emission of desulfurization wastewater and byproducts thereof, namely desulfurization sludge, through continuous treatment of the desulfurization wastewater and the desulfurization sludge, has short treatment period, high efficiency and good effect, is favorable for recycling heavy metals, salt-containing solid powder and sludge solids, is environment-friendly, and has no secondary pollution.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings are included to provide a further understanding of embodiments of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain, without limitation, the embodiments of the invention. In the drawings:
FIG. 1 is a schematic diagram of an industrial treatment system for desulfurization wastewater in a coal-fired power plant according to a fifth embodiment of the present invention;
fig. 2 is a schematic structural view of a separator according to a fifth embodiment of the present invention;
FIG. 3 is a schematic view of a filtration membrane according to a fifth embodiment of the present invention;
fig. 4 is a schematic flow chart of an industrial treatment method for desulfurization wastewater in a coal-fired power plant according to a fifth embodiment of the present invention.
Description of the reference numerals
The device comprises a 1-flue gas channel, a 2-dry ice cooling device, a 3-online detection module I, a 4-stirrer I, a 5-desulfurization wastewater reaction tank, a 6-first raw material tank, a 7-second raw material tank, a 8-third raw material tank, a 9-fourth raw material tank, a 10-stirrer II, a 11-online detection module II, a 12-primary filter, a 13-secondary filter, a 14-heavy metal recovery tank, a 15-stirrer III, a 16-fifth raw material tank, a 17-online detection module III, a 18-flue gas outlet pipe, a 19-chelating agent preparation tank, a 20-neutralization reaction tank, a 21-separator, a 22-online detection module IV, a 23-salt solution recovery tank, a 24-sixth raw material tank, a 25-desulfurization sludge treatment tank, a 26-stirrer IV, a 27-online detection module V, a 28-concentration evaporation drying tower, a 29-stirrer V, a 30-online detection module VI, a 31-seventh raw material tank, a 32-desulfurization sludge dewatering tank, a 201-centrifugal precipitator, a 202-filtration membrane, a 203-water pump, a 204-containing salt-202205, a 2021-micron stainless steel filtration membrane, a 2-grade ultrafiltration membrane and a 3-ultrafiltration membrane.
Detailed Description
The following describes the detailed implementation of the embodiments of the present invention with reference to the drawings. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
In the present invention, unless otherwise indicated, terms of orientation such as "upper, lower, top, bottom" are used generally with respect to the orientation shown in the drawings or with respect to the positional relationship of the various components with respect to one another in the vertical, vertical or gravitational directions. The "first," "second," etc. are merely for convenience of description and for convenience of distinction, and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should also be noted that, unless explicitly specified and limited otherwise, the terms "mounted," "connected," and the like are to be construed broadly and may be, for example, fixedly connected, detachably connected, or integrally connected; can be directly connected or indirectly connected; either a wired connection or a wireless connection. The specific meaning of the above terms in the present invention can be understood as appropriate by those of ordinary skill in the art.
The invention will be described in detail below with reference to the drawings in connection with embodiments.
Example 1
The first embodiment of the invention provides a heavy metal ion chelating agent and a preparation method thereof. Specifically, the preparation method of the heavy metal ion chelating agent can comprise the following steps:
step S101: according to a first predetermined massWeighing 4-amino-3-phenylbutyrate, DL-3, 4-dihydroxyphenyl glycol, 4' -dichloro diphenyl sulfone and nano SiO 2 Modified polyacrylic resin.
Here, 4-amino-3-phenylbutyrate, DL-3, 4-dihydroxyphenyl diol, 4' -dichlorodiphenyl sulfone and nano SiO 2 The first predetermined mass ratio of the modified polyacrylic resin may be (1.2 to 3.5) to (2.1 to 3.8): (1.4 to 2.5): (5.0 to 9.5).
Further, in one possible embodiment, 4-amino-3-phenylbutyrate hydrochloride, DL-3, 4-dihydroxyphenyl diol, 4' -dichlorodiphenyl sulfone, and nano SiO 2 The first predetermined mass ratio of the modified polyacrylic resin may also be: 2.1:2.5:1.8:6.2.
step S102: 4-amino-3-phenylbutyrate, DL-3, 4-dihydroxyphenyl glycol, 4' -dichloro diphenyl sulfone and nano SiO 2 And mixing the modified polyacrylic resin, and continuously stirring until each reactant is subjected to chelation reaction to prepare the heavy metal ion chelating agent.
Here, the stirring time of each reactant may be set to 30min to 60min to improve the reaction efficiency.
During the process of preparing the heavy metal ion chelating agent, nano SiO is added 2 The purpose of the modified polyacrylic resin is to be used as a framework material. Nano SiO 2 Has spherical microstructure and flocculent and net structure, and the DL-3, 4-dihydroxyphenyl glycol contains abundant hydroxyl groups, so after the DL-3, 4-dihydroxyphenyl glycol is added, the hydroxyl groups in the DL-3, 4-dihydroxyphenyl glycol can be combined with nano SiO 2 Nano SiO in modified polyacrylic resin 2 The reaction generates silicon hydroxyl group which is successfully loaded on the nano SiO 2 The flocculent and netlike pores on the surface of the modified polyacrylic resin. Meanwhile, the 4-amino-3-phenylbutyrate added in the reaction process contains amino functional groups, and the existence of the amino functional groups can promote the stable loading of the 4-amino-3-phenylbutyrate on the nano SiO 2 The flocculent and netlike pores on the surface of the modified polyacrylic resin. In addition, the purpose of adding 4,4' -dichlorodiphenyl sulfone during the reaction is to serve as an auxiliary agent,for improving the reaction rate and improving the load stability.
The 4-amino-3-phenylbutyrate used in step S101 and step S102 is a chemical substance having the chemical formula C 10 H 14 ClNO 2 。
The DL-3, 4-dihydroxyphenyl diols used in step S101 and step S102 are a chemical substance having the chemical formula C 8 H 10 O 4 。
The 4,4' -dichlorodiphenyl sulfone used in step S101 and step S102 is a chemical substance having the chemical formula C 12 H 8 Cl 2 O 2 S。
Nano SiO employed in step S101 and step S102 2 The modified polyacrylic resin is prepared by using nano SiO 2 The preparation method of the prepared chemical substance comprises the following steps: to nano SiO 2 Adding silane coupling agent DL602 into nano SiO 2 Modifying the surface, adding polyacrylic resin, and preparing nano SiO by blending and in-situ polymerization 2 Modified polyacrylic resin.
The embodiment also provides a heavy metal ion chelating agent, which can be obtained by the preparation method.
The heavy metal ion chelating agent prepared by the embodiment has higher adsorption capacity for heavy metal ions, can strongly adsorb the heavy metal ions, and can be used for removing the heavy metal ions (e.g. Cr 2+ 、Ni 2+ 、Cu 2+ 、Zn 2+ 、As 2 + 、Cd 2+ 、Pb 2+ 、Hg 2+ Equal heavy metal ions), and the removal rate of each heavy metal ion is close to 100 percent. In addition, the novel heavy metal ion chelating agent prepared by the embodiment is environment-friendly, can not generate other additional influences on the environment, and can not cause secondary pollution.
Example two
In order to demonstrate the reliability and adsorption effect of the heavy metal ion chelating agent of the present invention, the second embodiment of the present invention conducted adsorption capacity test for the heavy metal ion chelating agent.
Specifically, the adsorption capacity test for the heavy metal ion chelating agent comprises the following steps:
step S201: weighing the mass asmThe novel heavy metal ion chelating agent is respectively added into a plurality of groups of heavy metal ion liquids, and is fully absorbed by constant-temperature oscillation at room temperature.
Here, the several groups of heavy metal ion liquids comprise the same volumeVAnd different concentrationsC 0 The method comprises the steps of carrying out a first treatment on the surface of the The novel heavy metal ion chelating agent is the heavy metal ion chelating agent prepared and obtained in the first embodiment.
Step S202: after filtration and separation, the adsorption equilibrium concentration of heavy metal ions in each group of solutions is measured by adopting inductively coupled plasma-atomic emission spectrometry (Inductively coupled plasma-atomic emission spectrometry, ICP-AES)C e 。
Wherein the adsorption amount of heavy metal ions at the time of balancingQ e The calculation is performed according to the following formula:
wherein,mis the quality of the novel heavy metal ion chelating agent,C 0 as an initial concentration of heavy metal ions,C e in order to adsorb the equilibrium concentration of the water,Vis the volume of the heavy metal ionic liquid.
The adsorption capacity of the heavy metal ion chelating agent prepared in the first embodiment on each heavy metal ion can be obtained through the above test process. As shown in Table 1, the heavy metal ion chelating agent prepared according to the first embodiment of the invention has a specific activity on Cr 2+ The adsorption capacity of (2) is 2.195mmol/g; for Ni 2+ The adsorption capacity of (2) is 2.894mmol/g; for Cu 2+ The adsorption capacity of (2) is 3.703mmol/g; for Zn 2+ Has an adsorption capacity of 2.281mmol/g; for As 2+ The adsorption capacity of (C) is 2.523mmol/g; for Cd 2+ Has an adsorption capacity of 2.595mmol/g; for Pb 2+ Has an adsorption capacity of 2.307mmol/g; for Hg 2+ The adsorption capacity of (C) was 2.467mmol/g.
TABLE 1 adsorption Capacity of heavy Metal ion chelators for heavy Metal ions
In addition, in order to verify the heavy metal ion removal capability of the heavy metal ion chelating agent prepared in the first embodiment of the invention, the second embodiment of the invention also adopts desulfurization wastewater to test the heavy metal ion removal capability of the heavy metal ion chelating agent.
Specifically, the heavy metal ion removal capability test for the heavy metal ion chelating agent includes the following procedures:
(1) 150mL of desulfurization wastewater for test is prepared firstly, and Cr in the wastewater is prepared 2+ 、Ni 2+ 、Cu 2+ 、Zn 2+ 、As 2+ 、Cd 2+ 、Pb 2+ And Hg of 2+ The concentration is 15mg/L.
(2) The heavy metal ion chelating agent prepared in the first example of the present invention was then added to the above-described desulfurization waste water for test. Wherein the concentration of the heavy metal ion chelating agent in the desulfurization wastewater for the test is 120mg/L.
(3) After stirring, standing for about 5min, filtering, and then measuring the concentration of the treated heavy metal ions by using an inductively coupled plasma mass spectrometry (IPC-MS). The results are shown in Table 2.
TABLE 2 removal Rate of heavy Metal ion chelating agent for various heavy Metal ions in desulfurization wastewater
As can be seen from the above test results, the heavy metal ion chelating agent prepared according to the first embodiment of the invention is specific to Cr 2+ 、Ni 2+ 、Cu 2+ 、Zn 2+ 、As 2+ 、Cd 2+ 、Pb 2+ 、Hg 2+ The equivalent heavy metal ions have stronger chelating coordination capacity and higher adsorption capacity for heavy metal ionsWhile being environmentally friendly to ions (such as Na + 、K + 、Ca 2+ Etc.) have substantially no chelating ability. Meanwhile, the heavy metal ion chelating agent prepared in the first embodiment of the invention has the following properties with respect to Cr 2+ 、Ni 2+ 、Cu 2+ 、Zn 2+ 、As 2+ 、Cd 2+ 、Pb 2+ 、Hg 2 + The removal rate of the equal heavy metal ions is close to 100%, and the equal heavy metal ion removal capacity is high.
Example III
A third embodiment of the present invention provides an industrial treatment system for desulfurization wastewater of a coal-fired power plant, which may include: the device comprises a chelating agent preparation unit, a desulfurization wastewater reaction unit, a filtering unit, a neutralization reaction unit, a solid-liquid separation unit, a desulfurization sludge treatment unit and a salt solution recovery unit.
Specifically, the chelating agent preparation unit is used for preparing 4-amino-3-phenylbutyrate hydrochloride, DL-3, 4-dihydroxyphenyl glycol, 4' -dichlorodiphenyl sulfone and nano SiO 2 The modified polyacrylic resin is prepared into heavy metal ion chelating agent. The chelating agent formulation unit is provided for the purpose of formulating and storing the novel heavy metal ion chelating agent of the invention.
For example, the chelating agent formulation unit may be composed of a first feedstock tank, a second feedstock tank, a third feedstock tank, a fourth feedstock tank, and a chelating agent formulation tank. Wherein the first raw material tank is used for storing 4-amino-3-phenylbutyrate; the second raw material tank is used for storing DL-3, 4-dihydroxyphenyl glycol; the third raw material tank is used for storing 4,4' -dichlorodiphenyl sulfone; the fourth raw material tank is used for storing nano SiO 2 Modified polyacrylic resin. The first raw material tank, the second raw material tank, the third raw material tank and the fourth raw material tank are respectively communicated with the inlet of the chelating agent preparation tank and are used for adding reactants required for preparing the heavy metal ion chelating agent into the chelating agent preparation tank. Chelating agent preparation tank for preparing 4-amino-3-phenylbutyrate, DL-3, 4-dihydroxyphenyl glycol, 4' -dichlorodiphenyl sulfone and nano SiO 2 The modified polyacrylic resin is prepared as heavy metal ion chelating agent according to a first predetermined mass ratio. Here, 4-amino-3-phenylbutyrateAcid salt, DL-3, 4-dihydroxyphenyl glycol, 4' -dichlorodiphenyl sulfone and nano SiO 2 The first preset mass ratio of the modified polyacrylic resin is (1.2-3.5) to (2.1-3.8): (1.4 to 2.5): (5.0 to 9.5).
The inlet of the desulfurization wastewater reaction unit is communicated with the outlet of the chelating agent preparation unit and is used for mixing the heavy metal ion chelating agent with the desulfurization wastewater and carrying out chelation reaction, so that heavy metal ions in the desulfurization wastewater are removed. The desulfurization wastewater reaction unit is arranged to provide a place for the chelating agent of heavy metal ions and desulfurization wastewater to carry out chelating reaction, so that the heavy metal ions in the desulfurization wastewater can be fully removed by the heavy metal ion chelating agent.
The inlet of the filtering unit is communicated with the outlet of the desulfurization wastewater reaction unit and is used for filtering flocculent precipitate in the desulfurization wastewater after the chelation reaction to obtain desulfurization wastewater after heavy metal ions are removed. Because the heavy metal ion chelating agent and heavy metal ions in the desulfurization wastewater generate a stable flocculent precipitate after undergoing a chelating reaction, the purpose of the filter unit is to remove the heavy metal flocculent precipitate carried by the desulfurization wastewater, so as to prevent the influence of the heavy metal flocculent precipitate on subsequent treatment operation and improve the treatment effect of the desulfurization wastewater. For example, the filter unit may consist of one or more filters.
The inlet of the neutralization reaction unit is communicated with the outlet of the filtering unit and is used for mixing alkaline substances with the desulfurization wastewater after heavy metal ions are removed and carrying out neutralization reaction to obtain the desulfurization wastewater after the pH value is regulated. The neutralization reaction unit is arranged for adjusting the pH value of the desulfurization wastewater, so that the pH value of the desulfurization wastewater is changed from 0-2 to 7-13, and the related emission standard requirement is met. The alkaline substance herein means a substance capable of reacting with H in desulfurization wastewater + The substance that undergoes the neutralization reaction may be, for example, calcium hydroxide, sodium hydroxide, or the like.
The inlet of the solid-liquid separation unit is communicated with the outlet of the neutralization reaction unit and is used for carrying out solid-liquid separation on the salt-containing slurry and the desulfurization sludge in the desulfurization wastewater with the pH value adjusted. The purpose of setting up solid-liquid separation unit is to realize the high-efficient separation of salt-containing slurry and desulfurization mud to follow-up carry out independent recovery processing to salt-containing slurry and desulfurization mud. For example, the solid-liquid separation unit may be a precipitator, a centrifuge, a filter cartridge, or a bag filter.
The inlet of the desulfurization sludge treatment unit is communicated with the sludge outlet of the solid-liquid separation unit and is used for removing the moisture content in the desulfurization sludge. The purpose of the desulfurization sludge treatment unit is to reduce the moisture content in the desulfurization sludge, thereby reducing the viscosity of the desulfurization sludge. For example, the desulfurization sludge treatment unit may employ a dewatering centrifuge, a screw dewatering machine, a belt centrifuge, or the like for achieving sludge dewatering by mechanical dewatering.
The inlet of the salt solution recovery unit is communicated with the salt solution outlet of the solid-liquid separation unit and is used for concentrating, evaporating and drying the salt-containing slurry to obtain salt-containing solid powder. The purpose of the brine recovery unit is to recover the brine slurry.
Further, in one possible embodiment, the industrial treatment system may further comprise a flue gas channel and a flue gas cooling unit on the basis of comprising a chelating agent preparation unit, a desulfurization wastewater reaction unit, a filtering unit, a neutralization reaction unit, a solid-liquid separation unit, a desulfurization sludge treatment unit and a salt solution recovery unit.
Specifically, the flue gas passageway is used for carrying the flue gas that coal fired power plant draught fan discharged, and the flue gas includes: carbon dioxide, sulfides, nitrogen oxides, air, soot, and ammonia. The inlet of the flue gas cooling unit is communicated with the flue gas channel and is used for cooling the temperature of the flue gas from 110 ℃ to 150 ℃ to 45 ℃ to 50 ℃. The outlet of the flue gas cooling unit is communicated with the inlet of the desulfurization wastewater reaction unit and is used for introducing cooled flue gas into the desulfurization wastewater.
The purpose of introducing low-temperature flue gas (namely, flue gas at 45-50 ℃) into the desulfurization wastewater is to keep the desulfurization wastewater in the desulfurization wastewater reaction unit at about 45-50 ℃, so that the reaction of the heavy metal ion chelating agent and the heavy metal ions is more complete. That is, the low-temperature flue gas is used as a catalyst to promote the reaction of the heavy metal ion chelating agent and the heavy metal ions in the desulfurization wastewater, so that the reaction rate is improved.
In addition, the flue gas humidified by the desulfurization wastewater in the desulfurization wastewater reaction unit can return to the flue gas channel through the flue gas outlet pipe, so that the recycling of the flue gas is realized.
Further, in one possible embodiment, the flue gas cooling unit may be composed of a dry ice storage tank and a dry ice injector. The dry ice ejector is arranged on the dry ice storage box, the inlet of the dry ice storage box is communicated with the flue gas channel, and the outlet of the dry ice storage box is communicated with the inlet of the desulfurization wastewater reaction unit.
Of course, the invention is not limited thereto, and other devices such as heat exchangers, cooling towers, sprayers, etc. may be applied to the flue gas cooling unit of the invention, as long as the flue gas cooling unit can meet the cooling treatment requirements of the flue gas of the coal-fired power plant.
Further, in one possible embodiment, the solid-liquid separation unit may be composed of a centrifugal precipitator, a filtration membrane and a suction pump. Wherein, the filtration membrane is transversely installed in the inside of centrifugal precipitator, and the filtration membrane comprises stainless steel filter screen, fiber filtration membrane and micron order milipore filter to stainless steel filter screen, fiber filtration membrane and micron order milipore filter are according to from down supreme setting up in proper order. The centrifugal precipitator is used for completing the separation of the salt-containing slurry and the desulfurization sludge, a salt solution outlet is arranged above the centrifugal precipitator, and a sludge outlet is arranged below the centrifugal precipitator. The inlet of the water pump is communicated with the salt solution outlet of the centrifugal precipitation machine, and the outlet of the water pump is communicated with the inlet of the salt solution recovery unit. The water suction pump is used for conveying the salt-containing slurry filtered by the filter membrane to the salt solution recovery unit so as to carry out subsequent salt-containing slurry recovery treatment.
Further, in one possible embodiment, the desulfurization sludge treatment unit may be composed of a fifth raw material tank, a sixth raw material tank, a desulfurization sludge treatment tank, and a desulfurization sludge dewatering tank. Wherein, the fifth raw material tank is used for storing modified calcium silicate slag; the sixth raw material tank is used for storing the dehydrating agent. The fifth raw material tank and the sixth raw material tank are respectively communicated with an inlet of a desulfurization sludge treatment tank, and the desulfurization sludge treatment tank is used for fully mixing the modified calcium silicate slag, the dehydrating agent and the desulfurization sludge. The desulfurization sludge dewatering tank is communicated with an outlet of the desulfurization sludge treatment tank and is used for mechanically dewatering the mixed desulfurization sludge.
The purpose of adding the modified calcium silicate slag into the desulfurization sludge is to physically combine the modified calcium silicate slag with the desulfurization sludge so as to maintain the porous structure of the desulfurization sludge and improve the permeability of the desulfurization sludge. Then on the basis, a dehydrating agent is added into the desulfurization sludge, so that the overall dehydration performance of the desulfurization sludge can be improved. Finally, the water content of the desulfurization sludge can be reduced to below 50% by combining mechanical dehydration, so that the viscosity of the desulfurization sludge is reduced.
Further, in one possible embodiment, the industrial treatment system may further comprise an on-line detection unit and a control unit on the basis of comprising a chelating agent preparation unit, a desulfurization wastewater reaction unit, a filtration unit, a neutralization reaction unit, a solid-liquid separation unit, a desulfurization sludge treatment unit and a salt solution recovery unit.
Specifically, the online detection unit may include a first detection module, a second detection module, a third detection module, a fourth detection module, a fifth detection module, and a sixth detection module. The first detection module is used for detecting the air pressure and the temperature in the desulfurization wastewater reaction unit. The second detection module is used for detecting the concentration of each reactant in the chelating agent preparation unit. The third detection module is used for detecting the pH value in the neutralization reaction unit. The fourth detection module is used for detecting the salt concentration in the solid-liquid separation unit. The fifth detection module is used for detecting the water content of the desulfurization sludge in the desulfurization sludge treatment unit. The sixth detection module is used for detecting the water content of the salt solution in the salt solution recovery unit.
The control unit is connected with the online detection unit and is used for receiving a plurality of detection data output by the online detection unit and outputting corresponding control decisions.
For example, after the control unit may receive the real-time air pressure value and the real-time temperature value transmitted by the first detection module, by judging whether the real-time air pressure value and the real-time temperature value conform to the corresponding preset threshold ranges, the control unit outputs a temperature control strategy and a pressure control strategy for the desulfurization wastewater reaction unit, so as to avoid the chelating reaction affecting the heavy metal ions due to too low or too high temperature.
The control unit can output the control strategy for the addition amount of each reactant aiming at the chelating agent preparation unit after receiving the concentration value of each reactant transmitted by the second detection module and judging whether the concentration value of each reactant accords with the corresponding preset threshold range, so that the effect of influencing the heavy metal ion chelating agent due to the excessive or insufficient addition amount of the reactant is avoided.
The control unit can receive the pH value transmitted by the third detection module, and output a termination reaction strategy aiming at the neutralization reaction unit after judging whether the pH value meets the corresponding standard emission requirement, so that the influence on the acidity and alkalinity of the desulfurization wastewater due to the excessive addition of alkaline substances is avoided.
The control unit can output the evaporation concentration strategy of the salt solution recovery unit to improve the treatment effect of the salt solution while realizing the effective monitoring of the salt solution recovery process after receiving the salt concentration value transmitted by the fourth detection module and the salt solution water content value transmitted by the sixth detection module.
The control unit can output the dehydration treatment strategy of the desulfurization sludge treatment unit to improve the treatment effect of the desulfurization sludge while realizing the effective monitoring of the desulfurization sludge treatment process after receiving the desulfurization sludge water content value transmitted by the fifth detection module.
Example IV
The fourth embodiment of the invention provides an industrialized treatment method of desulfurization wastewater of a coal-fired power plant, which is realized by the industrialized treatment system in the third embodiment of the invention and comprises the following steps:
step S401: adding a heavy metal ion chelating agent into the desulfurization wastewater, and carrying out chelation reaction on the heavy metal ion chelating agent and heavy metal ions in the desulfurization wastewater by continuous stirring to generate desulfurization wastewater with flocculent precipitate.
Here, the heavy metal ion chelating agent may be prepared by: sequentially adding 4-amino-3-phenylbutyrate, DL-3, 4-dihydroxyphenyl glycol, 4' -dichlorodiphenyl sulfone and nano SiO into a chelating agent preparation tank 2 Modified polyacrylic resin and control of nano SiO 2 The heavy metal ion chelating agent is prepared by stirring the modified polyacrylic resin, 4-amino-3-phenylbutyrate, DL-3, 4-dihydroxyphenyl glycol and 4,4' -dichlorodiphenyl sulfone according to a first preset mass ratio of (5.0-9.5) to (1.2-3.5) to (2.1-8) to (1.4-2.5) for 30-60 min.
Step S402: filtering flocculent precipitate in the desulfurization wastewater after the chelation reaction to obtain desulfurization wastewater after heavy metal ions are removed.
Step S403: adding alkaline substances into the desulfurization wastewater from which heavy metal ions are removed, and carrying out neutralization reaction on the alkaline substances and the desulfurization wastewater by continuous stirring to obtain the desulfurization wastewater with the pH value of 7-13.
Step S404: and carrying out solid-liquid separation on the desulfurization wastewater with the pH value of 7-13 to respectively obtain salt-containing slurry and desulfurization sludge.
Step S405: removing the moisture content in the desulfurization sludge.
Step S406: concentrating, evaporating and drying the salt-containing slurry to obtain salt-containing solid powder.
Further, in one possible embodiment, the low-temperature flue gas may be introduced into the desulfurization wastewater while the heavy metal ion chelating agent is added into the desulfurization wastewater, so as to promote the chelation reaction between the heavy metal ion chelating agent and the heavy metal ions in the desulfurization wastewater.
Specifically, step S401 may be refined into sub-steps S4011 to S4013 described below.
Substep S4011: and cooling the flue gas discharged by the coal-fired power plant to obtain low-temperature flue gas with the temperature of 45-50 ℃.
Sub-step S4012: and adding the heavy metal ion chelating agent into the desulfurization wastewater, and simultaneously, introducing low-temperature flue gas into the desulfurization wastewater.
Sub-step S4013: the mixture of heavy metal ion chelating agent and desulfurization wastewater is fully stirred until desulfurization wastewater with flocculent precipitate is generated.
Further, in one possible embodiment, the process of removing the moisture content in the desulfurization sludge includes, but is not limited to, substeps S4051 to S4053 described below.
Substep S4051: and adding the modified calcium silicate slag into the desulfurization sludge, and stirring for 5-8 min to ensure that all the substances are fully mixed.
Substep S4052: and adding a dehydrating agent into the desulfurization sludge mixed with the modified calcium silicate slag, and stirring for 5-8 min to ensure that all the substances are fully mixed.
Substep S4053: and mechanically dehydrating the desulfurization sludge mixed with the modified calcium silicate slag and the dehydrating agent to obtain the desulfurization sludge with the moisture content lower than 50%.
The second preset mass ratio of the solid phase substances in the modified calcium silicate slag and the desulfurization sludge can be (0.1-0.3) to (1-1.2); the third preset mass ratio of the dehydrating agent to the solid phase substance in the desulfurization sludge is (0.05-0.1) to (1-1.2). The dehydrating agent used may be Polyacrylamide (PAM).
In the early stage of the dehydration treatment of the desulfurization sludge, the modified calcium silicate slag is physically combined with the desulfurization sludge to maintain the porous structure of the desulfurization sludge, so that the permeability of the desulfurization sludge is improved, then the whole dehydration performance of the desulfurization sludge is improved through a dehydrating agent, and finally the moisture content of the desulfurization sludge can be reduced to below 50% by combining with mechanical dehydration, so that the viscosity of the desulfurization sludge is reduced.
Example five
A fifth embodiment of the present invention provides an industrial treatment system for desulfurization wastewater of a coal-fired power plant, as shown in fig. 1, which may include: a flue gas channel 1, a dry ice cooling device 2, an online detection module one 3, a stirrer one 4, a desulfurization wastewater reaction tank 5, a first raw material tank 6, a second raw material tank 7, a third raw material tank 8, a fourth raw material tank 9, a stirrer two 10, an online detection module two 11, a primary filter 12, a secondary filter 13, a heavy metal recovery tank 14, a stirrer three 15, a fifth raw material tank 16, an online detection module three 17, a flue gas outlet pipe 18, a chelating agent preparation tank 19, a neutralization reaction tank 20, a separator 21, an online detection module four 22, a salt solution recovery tank 23, a sixth raw material tank 24, a desulfurization sludge treatment tank 25, a stirrer four 26, an online detection module five 27, a concentrated evaporation drying tower 28, a stirrer five 29, an online detection module six 30, a seventh raw material tank 31 and a desulfurization sludge dewatering tank 32.
The flue gas channel 1 is connected with the dry ice cooling device 2, the dry ice cooling device 2 is connected with the desulfurization waste water reaction tank 5, and the desulfurization waste water reaction tank 5 is also connected with the flue gas channel 1 through a flue gas outlet pipe 18. The dry ice cooling device 2 can be composed of a dry ice storage box and a dry ice ejector, wherein the dry ice ejector is arranged on the dry ice storage box, the inlet of the dry ice storage box is connected with the flue gas channel 1, and the outlet of the dry ice storage box is connected with the desulfurization wastewater reaction tank 5. The desulfurization wastewater reaction tank 5 is provided with an on-line detection module I3 and a stirrer I4. The on-line detection module I3 is used for detecting the air pressure and the temperature in the desulfurization wastewater reaction tank 5 in real time; the stirrer I4 is used for stirring the desulfurization wastewater and the heavy metal ion chelating agent in the desulfurization wastewater reaction tank 5 so as to improve the reaction rate.
The outlet of the chelating agent preparation tank 19 is connected with the inlet of the desulfurization wastewater reaction tank 5, and the first raw material tank 6, the second raw material tank 7, the third raw material tank 8 and the fourth raw material tank 9 are all arranged on the chelating agent preparation tank 19, and the chelating agent preparation tank 19 is also provided with an online detection module II 11 and a stirrer II 10. And, the metering pump is all installed to the discharge gate of head tank 6, head tank 7 No. two, head tank 8 No. three and head tank 9 No. four, head tank 6 No. two, head tank 7 No. three, head tank 8 No. three and head tank 9 No. four on the metering pump all link to each other with on-line measuring module two 11. The online detection module II 11 is used for monitoring the concentration of each reactant in the preparation process in real time, and preventing excessive addition of certain reactants, thereby affecting the effect of the heavy metal ion chelating agent. The second agitator 10 is used to agitate the reactants in the chelant formulation tank 19 sufficiently to increase the reaction rate.
Wherein, the first raw material tank 6 stores 4-amino-3-phenylbutyrate, the second raw material tank 7 stores DL-3, 4-dihydroxyphenyl glycol, and the third raw material tank 8Storing 4,4' -dichloro diphenyl sulfone, and storing nano SiO in a No. four raw material tank 9 2 Modified polyacrylic resin.
The inlet of the primary filter 12 is connected with the outlet of the desulfurization wastewater reaction tank 5, and the outlet of the primary filter 12 is respectively connected with the inlet of the secondary filter 13 and the heavy metal recovery tank 14. The outlet of the secondary filter 13 is connected to the inlet of the heavy metal recovery tank 14, and at the same time, the outlet of the secondary filter 13 is also connected to the inlet of the neutralization reaction tank 20. The heavy metal recovery tank 14 is used for recovering the flocculated precipitate after filtration.
The stirrer III 15, the raw material tank V16 and the online detection module III 17 are all arranged on the neutralization reaction tank 20. The fifth raw material tank 16 stores calcium hydroxide therein, and a metering pump is installed at a discharge port of the fifth raw material tank 16. In addition, the metering pump on the fifth raw material tank 16 is connected with a third on-line detection module 17, and the third on-line detection module 17 is used for detecting the pH value in the neutralization reaction tank 20 in real time. The third stirrer 15 is used for fully stirring the desulfurization wastewater in the neutralization reaction tank 20 and the calcium hydroxide so as to improve the reaction efficiency. The outlet of the neutralization reaction tank 20 is connected to the inlet of the separator 21 for introducing the desulfurization wastewater after the neutralization reaction to the separator.
The outlet of the lower end of the separator 21 is connected with the inlet of the desulfurization sludge treatment tank 25, and the outlet of the desulfurization sludge treatment tank 25 is connected with the inlet of the desulfurization sludge dewatering tank 32. An on-line detection module four 22 is mounted on the separator 21 for real-time salt concentration in the separator 21. The sixth raw material tank 24, the fourth agitator 26, and the seventh raw material tank 31 are mounted on the desulfurization sludge treatment tank 25. Modified calcium silicate slag is stored in a No. six raw material tank 24, and a dehydrating agent is stored in a No. seven raw material tank 31. Metering pumps are mounted at the discharge port of the sixth raw material tank 24 and the discharge port of the seventh raw material tank 31. The online detection module five 27 is installed on the desulfurization sludge dewatering tank 32 and is used for detecting the moisture content of the desulfurization sludge in the desulfurization sludge dewatering tank 32 in real time.
The upper outlet of the separator 21 is connected to the inlet of the brine recovery tank 23, and the outlet of the brine recovery tank 23 is connected to the inlet of the concentrating, evaporating and drying tower 28. The stirrer five 29 and the on-line detection module six 30 are both installed on the concentrated evaporation drying tower 28. The agitator five 29 is used to agitate the salt-containing slurry to increase the reaction rate. The online detection module six 30 is used for detecting the moisture content in the concentrated evaporation drying tower 28 in real time.
As shown in fig. 2, the separator 21 is composed of a centrifugal precipitator 201, a filtration membrane 202, and a water pump 203. Wherein, the filter membrane 202 is transversely arranged at one third of the upper end of the inside of the centrifugal precipitator 201, the outlet of the centrifugal precipitator 201 is provided with a water pump 203, and the outlet of the high-power water pump 203 is connected with the inlet of the salt solution recovery tank 23. After the centrifugal sedimentation machine is started to start centrifugal sedimentation operation, the lower end of the centrifugal sedimentation machine 201 is a centrifugal sedimentation part, namely desulfurization sludge 205; at the upper end of the centrifugal settler 201 is a centrifugal liquid fraction, i.e. a salt-containing slurry 204.
After the separator is started, the centrifugal sedimentation machine starts to carry out centrifugal sedimentation operation, centrifugation is carried out for 10-15min each time, after centrifugation is stopped, the lower end of the centrifugal sedimentation machine is desulfurized sludge, and the upper end of the centrifugal sedimentation machine is salt-containing slurry. And after centrifugal precipitation is finished, the filtering membrane is installed, and the filtering membrane is installed at one third of the upper end of the inside of the centrifugal precipitation machine as much as possible, so that the filtering operation is convenient. At the moment, the high-power water suction pump is started to suck the salt-containing slurry at the upper end of the centrifugal precipitation machine into the salt solution recovery tank. Under the action of a high-power water suction pump, the salt-containing slurry at the middle and lower ends in the centrifugal precipitation machine is filtered by a filtering membrane firstly to remove impurities such as sludge and then pumped into a salt solution recovery tank, so that the water content of the residual desulfurization sludge is reduced while the salt-containing slurry is purified.
As shown in fig. 3, in order to enhance the filtering effect of the filtering membrane, the filtering membrane 202 may be composed of a stainless steel filtering screen 2021, a fiber filtering membrane 2022, and a micro-scale ultrafiltration membrane 2023. Wherein, the stainless steel filter screen 2021, the fiber filter membrane 2022 and the micron-sized ultrafiltration membrane 2023 are sequentially arranged from bottom to top. The stainless steel filter screen is used for filtering out solid particles with the same size as dust, filtering out solid particles with medium size which are not filtered out by the stainless steel filter screen through the fiber filter membrane, and finally filtering out fine particles with the same size as bacteria through the micron-sized ultrafiltration membrane without filtering out salt components.
Further, the industrial processing system can further comprise a control unit, and the first online detection module, the second online detection module, the third online detection module, the fourth online detection module, the fifth online detection module and the sixth online detection module are all connected with the control unit. The on-line detection module I is used for uploading the detected air pressure value and temperature value in the desulfurization wastewater reaction tank to the control unit in real time; the online detection module II is used for uploading the detected concentration of each reactant in the chelating agent preparation tank to the control unit in real time; the online detection module III is used for uploading the detected pH value in the neutralization reaction tank to the control unit in real time; the online detection module is used for uploading the detected salt concentration value in the separator to the control unit in real time; the online detection module is used for uploading the detected moisture content value of the desulfurization sludge in the desulfurization sludge dehydration tank to the control unit in real time; and the online detection module six is used for uploading the detected moisture content value in the concentrated evaporation drying tower to the control unit in real time. The control unit receives the data uploaded by each online detection module, processes the data respectively, gives out corresponding control decisions, and realizes intelligent monitoring of desulfurization wastewater treatment.
The fifth embodiment of the present invention also provides an industrial treatment method for desulfurization wastewater of a coal-fired power plant, which is implemented by the above-mentioned industrial treatment system, as shown in fig. 4, and includes the following steps:
step S501: and cooling the flue gas at the outlet of the induced draft fan of the coal-fired power plant.
The temperature of the flue gas at the outlet of the induced draft fan of the coal-fired power plant is generally about 110-150 ℃, and the temperature range of the flue gas to be used in the embodiment is about 50 ℃, so that the flue gas at the outlet of the induced draft fan of the coal-fired power plant needs to be cooled in the first step.
Specifically, firstly, the dry ice cooling device is arranged on an air inlet pipeline between the flue gas channel and the desulfurization wastewater reaction tank, and then the dry ice cooling device is started to cool flue gas in the flue gas channel, so that the temperature of the flue gas is reduced to 50 ℃. The flue gas introduced into the desulfurization wastewater reaction tank returns to the flue gas channel through the flue gas outlet pipe to realize cyclic utilization.
And the flue gas of the coal-fired power plant enters the dry ice cooling device through the flue gas channel and the pipeline to be cooled, and when the temperature is reduced, the dry ice ejector is started to realize the cooling treatment of the flue gas of the coal-fired power plant. The flue gas of the coal-fired power plant after cooling can keep the temperature of the desulfurization wastewater in the desulfurization wastewater reaction tank at about 50 ℃, so that the reaction of the heavy metal ion chelating agent and the heavy metal ions is more complete and thorough. In other words, the flue gas of the coal-fired power plant introduced in the step is mainly used as a catalyst for the heavy metal chelation reaction in the step S503, and is used for accelerating the heavy metal chelation reaction and improving the effect of the heavy metal chelation reaction, so that the efficiency of overall desulfurization wastewater treatment is improved, and the removal rate of heavy metal ions is improved.
Here, the coal-fired power plant flue gas mainly comprises the following components: carbon dioxide, sulfides (sulfur dioxide, sulfur trioxide), NOx oxides, air, soot (containing heavy metal particles) and partially escaped ammonia.
In addition, in the process of carrying out flue gas temperature reduction of the coal-fired power plant and introducing the desulfurization waste water reaction tank, the air pressure and the temperature in the desulfurization waste water reaction tank are detected in real time through the on-line detection module I, the detected air pressure value and the detected temperature value are uploaded to the control unit in real time, the air pressure and the temperature in the cooling process can be monitored in real time through the on-line detection module I, the real-time monitoring of the cooling process is realized, the chelating reaction of heavy metals is prevented from being influenced due to the fact that the temperature is too low or too high, and the effect of the heavy metal chelating reaction is further improved.
Step S502: and preparing the heavy metal ion chelating agent.
Specifically, a first raw material tank, a second raw material tank, a third raw material tank, a fourth raw material tank and corresponding metering pumps are sequentially started, and 4-amino-3-phenylbutyrate, DL-3, 4-dihydroxyphenyl glycol, 4' -dichlorodiphenyl sulfone and nano SiO are sequentially added into a chelating agent preparation tank 2 Modifying the polyacrylic resin to obtain 4-amino-3-phenylbutyrate, DL-3, 4-dihydroxyphenyl glycol, 4' -dichlorodiphenyl sulfone and nano SiO 2 The modified polyacrylic resin reacts to prepare the high-efficiency heavy metal ion chelating agent.
In the reaction process, the second stirrer can be started to stir for 30-60 min so as to improve the reaction efficiency. Meanwhile, the concentration of each reactant in the chelating agent preparation tank is detected in real time through the on-line detection module II, and the detected concentration of each reactant is uploaded to the control unit in real time. The concentration of each reactant in the reaction process is monitored in real time through the online detection module II, so that the addition amount of each reactant can be effectively monitored, excessive addition of certain reactants is prevented, the effect of the heavy metal ion chelating agent is affected, and the preparation precision of the heavy metal ion chelating agent is improved.
Wherein, nano SiO 2 The first predetermined mass ratio of the modified polyacrylic resin, the 4-amino-3-phenylbutyrate, the DL-3, 4-dihydroxyphenyl glycol and the 4,4' -dichlorodiphenyl sulfone is as follows: (5.0-9.5) to (1.2-3.5) to (2.1-3.8) to (1.4-2.5). Preferably, nano SiO 2 The first predetermined mass ratio of the modified polyacrylic resin, the 4-amino-3-phenylbutyrate, the DL-3, 4-dihydroxyphenyl glycol and the 4,4' -dichlorodiphenyl sulfone is as follows: 6.2:2.1:2.5:1.8.
Step S503: adding a heavy metal ion chelating agent and the flue gas subjected to cooling treatment into the desulfurization wastewater to cause the heavy metal ion chelating agent to carry out chelation reaction with the heavy metal ions in the desulfurization wastewater.
Specifically, the prepared heavy metal ion chelating agent is added into a desulfurization wastewater reaction tank, and coal-fired power plant flue gas at 50 ℃ is introduced, so that the heavy metal ion chelating agent and heavy metal ions in desulfurization wastewater are subjected to chelation reaction, and a stable flocculent precipitate is formed between the heavy metal ion chelating agent and the heavy metal ions, so that Cr in the desulfurization wastewater is removed 2+ 、Ni 2+ 、Cu 2+ 、Zn 2+ 、As 2+ 、Cd 2+ 、Pb 2+ 、Hg 2+ And (3) an isoparaffinic metal ion. In the reaction process of the heavy metal ion chelating agent and the heavy metal ions in the desulfurization wastewater, the nano SiO is used for preparing the catalyst 2 The flocculent and netlike pores on the surface of the modified polyacrylic resin are loaded with DL-3, 4-dihydroxyphenyl glycol and 4-amino-3-phenylbutyrate, and the DL-3, 4-dihydroxyphenyl glycol and the 4-amino-3-phenylbutyrate both contain hydroxyl OH - 4-amino-3-phenylbutyrate hydrochlorideAt the same time contain amino, amino-NH 2 And hydroxyl-OH is used as a ligand, so that heavy metal ions can be fully chelated, the adsorbed heavy metal ions are not easy to fall off, and the heavy metal ion removal rate is improved.
In this step, modified nano SiO is used 2 Modified polyacrylic resin, DL-3, 4-dihydroxyphenyl glycol and 4-amino-3-phenylbutyrate are modified on nano SiO 2 The flocculent and reticular pores on the surface of the modified polyacrylic resin are internally coordinated and complexed with the coordination atoms such as N, O and the heavy metal ions to adsorb the heavy metal ions, so that the heavy metal ions in the desulfurization wastewater can be effectively adsorbed, the heavy metal ion removal rate is improved, the subsequent desulfurization sludge treatment process is simplified, and the desulfurization sludge treatment and recycling are facilitated.
Step S504: and (5) filtering the heavy metal flocculation precipitation.
Specifically, the desulfurization wastewater reacted in the desulfurization wastewater reaction tank and flocculent precipitate in the desulfurization wastewater reaction tank are introduced into a primary filter for primary filtration, and then the heavy metal flocculent precipitate obtained after the primary filtration is introduced into a heavy metal recovery tank for recovery treatment. Meanwhile, the desulfurization wastewater obtained after filtration is led into a secondary filter for secondary filtration, then the heavy metal flocculent precipitate obtained after secondary filtration is led into a heavy metal recovery tank for recovery treatment, and meanwhile, the desulfurization wastewater obtained after filtration is led into a neutralization reaction tank for neutralization reaction.
Step S505: the pH value of the desulfurization wastewater is adjusted through neutralization reaction.
Specifically, a fifth raw material tank is opened, calcium hydroxide stored in the fifth raw material tank is put into a neutralization reaction tank, so that the calcium hydroxide and desulfurization wastewater after heavy metal ions are removed are subjected to neutralization reaction, and impurities in the desulfurization wastewater are subjected to condensation under the action of the calcium hydroxide. In the neutralization reaction process, stirring is carried out by a stirrer III, so that the reaction efficiency is improved; meanwhile, the pH value in the neutralization reaction tank is detected in real time through the online detection module III, and the detected pH value is uploaded to the control unit in real time. The reaction can be timely terminated by detecting the pH value in the neutralization reaction tank in real time, so that the excessive addition of calcium hydroxide is avoided, the acid-base property of the desulfurization wastewater is influenced, and the intellectualization of the industrial treatment of the desulfurization wastewater is improved.
After the neutralization reaction, the acidity of the desulfurization waste water is reduced, the pH value of the desulfurization waste water is improved, the pH value of the desulfurization waste water is changed from 0-2 to 7-13, and the standard requirement is met.
Step S506: separating the salt-containing slurry from the desulfurization sludge.
Since salt-containing slurry and desulfurization sludge are formed after the neutralization reaction, solid-liquid separation by a separator is required. In the separation process, the salt concentration in the separator can be detected in real time through the on-line detection module IV, and the detected salt concentration value is uploaded to the control unit in real time. The salt concentration detected by the on-line detection module IV can be mastered at any time, so that the next operation is convenient, and the intellectualization of the industrial treatment of the desulfurization wastewater is improved.
Step S507: and (5) dehydrating the desulfurization sludge.
The desulfurization sludge after solid-liquid separation has high internal water content, so that further treatment is required. Firstly, introducing desulfurization sludge into a desulfurization sludge treatment tank, then sequentially opening a No. six raw material tank and a No. seven raw material tank, putting desulfurization sludge treatment agent (i.e. modified calcium silicate slag and dehydrating agent) into the desulfurization sludge treatment tank, and carrying out high-efficiency treatment on the desulfurization sludge under the action of the desulfurization sludge treatment agent.
The method comprises the following steps: firstly, adding modified calcium silicate slag, and then starting a stirrer IV to stir for 5-8 min so as to ensure that all substances are fully mixed, so that the modified calcium silicate slag serving as a rigid support can keep the porous structure of the desulfurization sludge, and the permeability of the desulfurization sludge is improved; then adding a dehydrating agent, starting a stirrer IV to stir for 5-8 min so as to ensure that all substances are fully mixed, thereby improving the overall dehydration performance of the desulfurization sludge; finally, combining mechanical dehydration, wherein the mechanical dehydration part is completed through a desulfurization sludge dehydration tank, and the moisture content of the desulfurization sludge is reduced to below 50 percent.
Wherein the second preset mass ratio of the added modified calcium silicate slag to the solid phase in the desulfurization sludge is (0.1-0.3) to (1-1.2); preferably, the second predetermined mass ratio of the added modified calcium silicate slag to the solid phase in the desulphurized sludge is 0.15:1.10.
The third preset mass ratio of the added dehydrating agent to the solid phase in the desulfurization sludge is (0.05-0.1) to (1-1.2), and preferably, the third preset mass ratio of the added dehydrating agent to the solid phase in the desulfurization sludge is 0.06:1.00.
The dehydrating agent used in this step may be Polyacrylamide (PAM).
In the treatment process, the moisture content of the desulfurization sludge in the desulfurization sludge dewatering tank is detected in real time through the online detection module five, and the detected moisture content value of the desulfurization sludge is uploaded to the control unit in real time, so that the effective monitoring of the moisture content of the desulfurization sludge is realized, and the desulfurization sludge treatment effect is improved.
Step S508: concentrating, evaporating and drying the salt-containing slurry.
Specifically, the salt-containing slurry after solid-liquid separation is introduced into a salt solution recovery tank, temporarily stored in the salt solution recovery tank, introduced into a concentration evaporation drying tower for concentration, evaporation and drying treatment, and finally salt-containing solid powder with the granularity of about 7-95 μm is formed.
In the processes of concentration, evaporation and drying, the moisture content in the concentration evaporation drying tower is detected in real time through an online detection module six, and the detected moisture content value is uploaded to the unit in real time. The water content generated in the concentration, evaporation and drying treatment processes can be detected in real time through the online detection module, so that the process of changing the salt-containing slurry into salt-containing solid powder can be effectively monitored, and the intellectualization of the industrial treatment of the desulfurization wastewater is improved. During the reaction, the stirrer five can be started to stir so as to increase the reaction rate.
The desulfurization waste water reaction tank in this embodiment corresponds to the desulfurization waste water reaction unit in the third embodiment of the present invention. The dry ice cooling device in this embodiment corresponds to the smoke cooling unit in the third embodiment of the present invention. The unit components constituted by the chelating agent preparing tank, the first raw material tank, the second raw material tank, the third raw material tank, and the fourth raw material tank in this embodiment correspond to the chelating agent preparing unit in the third embodiment of the present invention. The unit assembly constituted by the primary filter, the secondary filter and the heavy metal recovery tank in this embodiment corresponds to the filtration unit in the third embodiment of the present invention. The unit assembly constituted by the fifth raw material tank and the neutralization reaction tank in this embodiment corresponds to the neutralization reaction unit in the third embodiment of the present invention. The separator in this embodiment corresponds to the solid-liquid separation unit in the third embodiment of the present invention. The unit assembly constituted by the brine recovery tank and the concentrated evaporation drying tower in this embodiment corresponds to the brine recovery unit in the third embodiment of the invention. The unit assembly constituted by the sixth raw material tank, the desulfurization sludge treatment tank, the seventh raw material tank, and the desulfurization sludge dewatering tank in this embodiment corresponds to the desulfurization sludge treatment unit in the third embodiment of the present invention.
In addition, the first raw material tank in the present embodiment corresponds to the first raw material tank in the third embodiment of the present invention; the second raw material tank in this embodiment corresponds to the second raw material tank in the third embodiment of the present invention; the third raw material tank in this embodiment corresponds to the third raw material tank in the third embodiment of the present invention; the fourth raw material tank in the present embodiment corresponds to the fourth raw material tank in the third embodiment of the present invention; the sixth raw material tank in the present embodiment corresponds to the fifth raw material tank in the third embodiment of the present invention; the seventh raw material tank in this embodiment corresponds to the sixth raw material tank in the third embodiment of the present invention.
The first detection module in the third embodiment of the present invention corresponds to the on-line detection module in the first embodiment of the present invention; the second online detection module in the present embodiment is equivalent to the second detection module in the third embodiment of the present invention; the third on-line detection module in the present embodiment is equivalent to the third detection module in the third embodiment of the present invention; the fourth on-line detection module in the present embodiment is equivalent to the fourth detection module in the third embodiment of the present invention; the fifth on-line detection module in the present embodiment corresponds to the fifth detection module in the third embodiment of the present invention; the sixth on-line detection module in the present embodiment corresponds to the sixth detection module in the third embodiment of the present invention.
Example six
In order to demonstrate the reliability and effect of the present invention, moisture content measurement was performed on dehydrated desulfurization sludge obtained in the fifth embodiment of the present invention.
Taking the dehydrated desulfurization sludge finally obtained in the step S507 of the fifth embodiment, and measuring the water content of the sludge by using an infrared rapid moisture meter. The result shows that the water content of the dehydrated desulfurization sludge obtained by the method is 40% -50%. The existing general dehydration treatment only can reach the water content of 60% -65%. Therefore, the water content of the sludge dewatering device is far lower than that of the prior general dewatering treatment, the water content of the sludge is further reduced while the urban sludge discharge standard is achieved, the viscosity of the sludge is greatly reduced, and the sludge is more beneficial to the subsequent environment-friendly reprocessing and reutilization of the sludge.
In addition, by the heavy metal ion chelating treatment of step S503 of the fifth embodiment, the heavy metal elements in the obtained desulfurization sludge are made almost zero, and zero emission of desulfurization wastewater and desulfurization sludge is realized.
The preferred embodiments of the present invention have been described in detail above with reference to the accompanying drawings, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
Claims (12)
1. An industrial treatment system for desulfurization wastewater of a coal-fired power plant, which is characterized by comprising: the device comprises a chelating agent preparation unit, a desulfurization wastewater reaction unit, a filtering unit, a neutralization reaction unit, a solid-liquid separation unit, a desulfurization sludge treatment unit and a salt solution recovery unit;
wherein the chelating agent preparation unit is used for preparing 4-amino-3-phenylbutyrate, DL-3, 4-dihydroxyphenyl glycol, 4' -dichlorodiphenyl sulfone and nano SiO 2 The modified polyacrylic resin is prepared into a heavy metal ion chelating agent;
the inlet of the desulfurization wastewater reaction unit is communicated with the outlet of the chelating agent preparation unit and is used for mixing a heavy metal ion chelating agent with desulfurization wastewater and carrying out chelating reaction;
The inlet of the filtering unit is communicated with the outlet of the desulfurization wastewater reaction unit and is used for filtering flocculent precipitate in the desulfurization wastewater subjected to the chelation reaction to obtain desulfurization wastewater after heavy metal ions are removed;
the inlet of the neutralization reaction unit is communicated with the outlet of the filtering unit and is used for mixing alkaline substances with the desulfurization wastewater after heavy metal ions are removed and carrying out neutralization reaction to obtain the desulfurization wastewater after the pH value is regulated;
the inlet of the solid-liquid separation unit is communicated with the outlet of the neutralization reaction unit and is used for carrying out solid-liquid separation on salt-containing slurry and desulfurization sludge in the desulfurization wastewater with the pH value adjusted;
the inlet of the desulfurization sludge treatment unit is communicated with the sludge outlet of the solid-liquid separation unit and is used for removing the moisture content in the desulfurization sludge;
and the inlet of the salt solution recovery unit is communicated with the salt solution outlet of the solid-liquid separation unit and is used for concentrating, evaporating and drying the salt-containing slurry to obtain salt-containing solid powder.
2. The industrial treatment system for desulfurization wastewater of a coal-fired power plant according to claim 1, wherein the chelating agent preparation unit comprises: a first feedstock tank, a second feedstock tank, a third feedstock tank, a fourth feedstock tank, and a chelating agent formulation tank;
The first raw material tank, the second raw material tank, the third raw material tank and the fourth raw material tank are respectively communicated with the inlet of the chelating agent preparation tank;
the first raw material tank is used for storing 4-amino-3-phenylbutyrate;
the second raw material tank is used for storing DL-3, 4-dihydroxyphenyl glycol;
the third raw material tank is used for storing 4,4' -dichloro diphenyl sulfone;
the fourth raw material tank is used for storing nano SiO 2 Modified polyacrylic resin;
the chelating agent preparation tank is used for preparing 4-amino-3-phenylbutyrate, DL-3, 4-dihydroxyphenyl glycol, 4' -dichlorodiphenyl sulfone and nano SiO 2 The modified polyacrylic resin is prepared into a heavy metal ion chelating agent according to a first preset mass ratio; wherein the 4-amino-3-phenylbutyrate, the DL-3, 4-dihydroxyphenyl diol, the 4,4' -dichlorodiphenyl sulfone and the nano SiO 2 The first preset mass ratio of the modified polyacrylic resin is (1.2-3.5) to (2.1-3.8): (1.4 to 2.5): (5.0 to 9.5).
3. The industrial treatment system for desulfurization wastewater of a coal-fired power plant according to claim 1, further comprising: a flue gas channel and a flue gas cooling unit;
The flue gas channel is used for conveying flue gas discharged by a coal-fired power plant induced draft fan, and the flue gas comprises: carbon dioxide, sulfides, nitrogen oxides, air, soot, and ammonia;
an inlet of the flue gas cooling unit is communicated with the flue gas channel and is used for cooling the flue gas to 45-50 ℃;
the outlet of the flue gas cooling unit is communicated with the inlet of the desulfurization wastewater reaction unit and is used for introducing cooled flue gas into the desulfurization wastewater.
4. The industrial treatment system for desulfurization wastewater of a coal-fired power plant according to claim 3, wherein the flue gas cooling unit comprises: a dry ice storage tank and a dry ice ejector; the dry ice ejector is arranged on the dry ice storage box, an inlet of the dry ice storage box is communicated with the flue gas channel, and an outlet of the dry ice storage box is communicated with an inlet of the desulfurization wastewater reaction unit.
5. The industrial treatment system for desulfurization wastewater of a coal-fired power plant according to claim 1, wherein the solid-liquid separation unit comprises: a centrifugal precipitator, a filtering membrane and a water pump;
the filtering membrane is transversely arranged in the centrifugal precipitation machine and comprises a stainless steel filtering screen, a fiber filtering membrane and a micron-sized ultrafiltration membrane which are arranged in sequence from bottom to top;
The inlet of the water pump is communicated with the salt solution outlet of the centrifugal precipitation machine, and the outlet of the water pump is communicated with the inlet of the salt solution recovery unit.
6. The industrial treatment system for desulfurization wastewater of a coal-fired power plant according to claim 1, wherein the desulfurization sludge treatment unit comprises: a fifth raw material tank, a sixth raw material tank, a desulfurization sludge treatment tank and a desulfurization sludge dehydration tank;
the fifth raw material tank is used for storing modified calcium silicate slag;
the sixth raw material tank is used for storing a dehydrating agent;
the fifth raw material tank and the sixth raw material tank are respectively communicated with an inlet of the desulfurization sludge treatment tank, and the desulfurization sludge treatment tank is used for fully mixing the modified calcium silicate slag, the dehydrating agent and the desulfurization sludge;
the desulfurization sludge dewatering tank is communicated with the outlet of the desulfurization sludge treatment tank and is used for mechanically dewatering the mixed desulfurization sludge.
7. The industrial treatment system for desulfurization wastewater of a coal-fired power plant according to claim 1, further comprising: the online detection unit includes: the device comprises a first detection module, a second detection module, a third detection module, a fourth detection module, a fifth detection module and a sixth detection module;
The first detection module is used for detecting the air pressure and the temperature in the desulfurization wastewater reaction unit;
the second detection module is used for detecting the concentration of each reactant in the chelating agent preparation unit;
the third detection module is used for detecting the pH value in the neutralization reaction unit;
the fourth detection module is used for detecting the salt concentration in the solid-liquid separation unit;
the fifth detection module is used for detecting the water content of the desulfurization sludge in the desulfurization sludge treatment unit;
the sixth detection module is used for detecting the water content of the salt solution in the salt solution recovery unit;
the control unit is used for receiving the multiple detection data output by the online detection unit and outputting corresponding control decisions.
8. A heavy metal ion chelating agent, wherein said heavy metal ion chelating agent comprises: 4-amino-3-phenylbutyrate, DL-3, 4-dihydroxyphenyl diol, 4' -dichlorodiphenyl sulfone and nano SiO 2 Modified polyacrylic resin;
wherein the 4-amino-3-phenylbutyrate, the DL-3, 4-dihydroxyphenyl diol, the 4,4' -dichlorodiphenyl sulfone and the nano SiO 2 The first preset mass ratio of the modified polyacrylic resin is (1.2-3.5) to (2.1-3.8): (1.4 to 2.5): (5.0 to 9.5).
9. An industrial treatment method of desulfurization wastewater of a coal-fired power plant, which is characterized by being realized by the industrial treatment system of desulfurization wastewater of the coal-fired power plant according to any one of claims 1 to 7, and comprising the following steps:
adding the heavy metal ion chelating agent in the method for preparing the desulfurization wastewater, wherein the heavy metal ion chelating agent is added into the desulfurization wastewater, and the heavy metal ion chelating agent and heavy metal ions in the desulfurization wastewater are subjected to chelation reaction through continuous stirring to generate desulfurization wastewater with flocculent precipitate;
filtering flocculent precipitate in the desulfurization wastewater after the chelation reaction to obtain desulfurization wastewater after heavy metal ions are removed;
adding alkaline substances into the desulfurization wastewater from which heavy metal ions are removed, and carrying out neutralization reaction on the alkaline substances and the desulfurization wastewater by continuous stirring to obtain desulfurization wastewater with the pH value of 7-13;
carrying out solid-liquid separation on the desulfurization wastewater with the pH value of 7-13 to respectively obtain salt-containing slurry and desulfurization sludge;
removing the moisture content in the desulfurization sludge;
concentrating, evaporating and drying the salt-containing slurry to obtain salt-containing solid powder.
10. The industrial treatment method for desulfurization wastewater from a coal-fired power plant according to claim 9, wherein the removal of moisture content in desulfurization sludge comprises: firstly, sequentially adding modified calcium silicate slag and a dehydrating agent into the desulfurization sludge, continuously stirring, and then mechanically dehydrating the mixed desulfurization sludge to obtain the desulfurization sludge with the moisture content lower than 50%.
11. The industrial treatment method of desulfurization wastewater of a coal-fired power plant according to claim 10, wherein the second predetermined mass ratio of solid phase substances in the modified calcium silicate slag and the desulfurization sludge is (0.1-0.3) to (1-1.2); the third preset mass ratio of the solid phase substances in the dehydrating agent to the desulfurization sludge is (0.05-0.1) to (1-1.2).
12. The industrial treatment method for desulfurization wastewater of a coal-fired power plant according to claim 9, wherein flue gas at 45-50 ℃ is introduced into the desulfurization wastewater in the process of chelating reaction between the heavy metal ion chelating agent and heavy metal ions in the desulfurization wastewater.
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