CN113716782A - Treatment process and device for wastewater from production of high-chlorine salt dye intermediate - Google Patents
Treatment process and device for wastewater from production of high-chlorine salt dye intermediate Download PDFInfo
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- CN113716782A CN113716782A CN202111065973.XA CN202111065973A CN113716782A CN 113716782 A CN113716782 A CN 113716782A CN 202111065973 A CN202111065973 A CN 202111065973A CN 113716782 A CN113716782 A CN 113716782A
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- Prior art keywords
- wastewater
- tank
- production
- dye intermediate
- salt dye
- Prior art date
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- 239000002351 wastewater Substances 0.000 title claims abstract description 121
- 238000000034 method Methods 0.000 title claims abstract description 45
- 230000008569 process Effects 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 32
- 230000003647 oxidation Effects 0.000 claims abstract description 96
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 96
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 57
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000002253 acid Substances 0.000 claims abstract description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 21
- 239000006228 supernatant Substances 0.000 claims abstract description 19
- 239000000701 coagulant Substances 0.000 claims abstract description 17
- 150000003841 chloride salts Chemical class 0.000 claims abstract description 13
- 238000004064 recycling Methods 0.000 claims abstract description 13
- 238000001704 evaporation Methods 0.000 claims abstract description 12
- 230000008020 evaporation Effects 0.000 claims abstract description 11
- 238000010612 desalination reaction Methods 0.000 claims abstract description 10
- 239000002244 precipitate Substances 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 238000001556 precipitation Methods 0.000 claims abstract description 8
- 235000011121 sodium hydroxide Nutrition 0.000 claims abstract description 7
- 238000010992 reflux Methods 0.000 claims abstract description 4
- 238000004062 sedimentation Methods 0.000 claims description 35
- 230000003197 catalytic effect Effects 0.000 claims description 33
- 239000010802 sludge Substances 0.000 claims description 24
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 20
- 238000003860 storage Methods 0.000 claims description 16
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 15
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 11
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 9
- 230000014759 maintenance of location Effects 0.000 claims description 9
- 229920002401 polyacrylamide Polymers 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 238000004090 dissolution Methods 0.000 claims description 3
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000013461 design Methods 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 3
- 238000004065 wastewater treatment Methods 0.000 abstract description 3
- 239000000975 dye Substances 0.000 description 27
- 239000000543 intermediate Substances 0.000 description 26
- 150000003839 salts Chemical class 0.000 description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 239000003513 alkali Substances 0.000 description 11
- 229910052742 iron Inorganic materials 0.000 description 11
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 11
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 11
- 230000009471 action Effects 0.000 description 10
- -1 iron ions Chemical class 0.000 description 9
- 239000006227 byproduct Substances 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000002920 hazardous waste Substances 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Inorganic materials [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229960004887 ferric hydroxide Drugs 0.000 description 6
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 238000012946 outsourcing Methods 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- FECNOIODIVNEKI-UHFFFAOYSA-N 2-[(2-aminobenzoyl)amino]benzoic acid Chemical class NC1=CC=CC=C1C(=O)NC1=CC=CC=C1C(O)=O FECNOIODIVNEKI-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 238000005189 flocculation Methods 0.000 description 3
- 230000016615 flocculation Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000004148 unit process Methods 0.000 description 3
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 2
- 150000004056 anthraquinones Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 150000001804 chlorine Chemical class 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 238000011033 desalting Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910001447 ferric ion Inorganic materials 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 238000006864 oxidative decomposition reaction Methods 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- PLAZTCDQAHEYBI-UHFFFAOYSA-N 2-nitrotoluene Chemical compound CC1=CC=CC=C1[N+]([O-])=O PLAZTCDQAHEYBI-UHFFFAOYSA-N 0.000 description 1
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 1
- ZPTVNYMJQHSSEA-UHFFFAOYSA-N 4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1 ZPTVNYMJQHSSEA-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000000980 acid dye Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- YUENFNPLGJCNRB-UHFFFAOYSA-N anthracen-1-amine Chemical compound C1=CC=C2C=C3C(N)=CC=CC3=CC2=C1 YUENFNPLGJCNRB-UHFFFAOYSA-N 0.000 description 1
- 150000001492 aromatic hydrocarbon derivatives Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 229950011260 betanaphthol Drugs 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 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
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 239000000982 direct dye Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- FPJQWFBQXIKMMP-UHFFFAOYSA-N phenyl nitrate Chemical compound [O-][N+](=O)OC1=CC=CC=C1 FPJQWFBQXIKMMP-UHFFFAOYSA-N 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F9/00—Multistage treatment of water, waste water or sewage
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/048—Purification of waste water by evaporation
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- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
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- 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
- C02F1/5281—Installations for water purification using chemical agents
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- C02F2201/00—Apparatus for treatment of water, waste water or sewage
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Abstract
The invention relates to a treatment process and a treatment device for high chloride salt dye intermediate production wastewater, and belongs to the technical field of dye intermediate production wastewater treatment. The invention comprises the following steps: (a) adjusting the pH value of the wastewater; (b) introducing the wastewater into a Fenton oxidation reactor, and adding hydrogen peroxide; (c) adding coagulant aid and liquid caustic soda into the wastewater for primary precipitation; (d) adding ozone into the wastewater; (e) carrying out electrocatalytic oxidation on the wastewater; (f) adding liquid caustic soda into the wastewater, then separating mud from water, and enabling the supernatant to enter a multi-effect evaporator for evaporation and desalination; and (c) refluxing the bottom precipitate to the step (a), adding acid to dissolve the bottom precipitate, and then feeding the bottom precipitate into a Fenton oxidation reactor for recycling. The treatment process disclosed by the invention is scientific and reasonable in design, the problem of high treatment cost of the wastewater of enterprises is continuously solved, the wastewater is recycled, and the economic benefit is higher; meanwhile, the invention provides a processing device which is simple and convenient to operate.
Description
Technical Field
The invention relates to a treatment process and a treatment device for high chloride salt dye intermediate production wastewater, and belongs to the technical field of dye intermediate production wastewater treatment.
Background
The dye industry is one of the important industries of the fine chemistry industry, is closely connected with a plurality of industries, and plays an important role in national economy of China. China is the biggest dye producing country in the world at present, and with the rapid development of the dye industry, the environmental protection problem is increasingly prominent. The three wastes generated in the dye manufacturing process, especially the waste water, are the main sources of the dye industry in China which becomes a polluted household. According to the general investigation of pollutants in all industries in China, the wastewater discharged by dye production accounts for about 1.5-2.0% of the total wastewater discharged in China every year. The dye wastewater has particularity and is characterized by large discharge amount, large toxicity, high organic concentration, high salt content, high chroma and high content of refractory compounds, thereby having great treatment difficulty. At present, some enterprises can not achieve the emission reaching the standard.
Generally, the dye intermediate wastewater has the following characteristics:
the pollutants in the wastewater are various. The waste water of dye and dye intermediate contains acid, alkali, salt, halogen, hydrocarbon, nitro compound, amine, dye and intermediate, and some of them also contain virulent benzidine, pyridine, ammonia, phenol, heavy metals mercury, cadmium and chromium.
② the concentration of organic matter is high. The CODCr value of the organic pollutants is generally more than 4000mg/L, and for acid dyes, direct dyes and edible dyes, the raw materials are usually provided with sulfonic acid groups and are easily soluble in water, so that the organic pollutants mostly exist in the waste liquid in a water-soluble state.
③ high salt content. The salt content in the wastewater can reach dozens to hundreds of g/L.
The use requirement of the dye promotes the development of the dye to the photolysis resistance, oxidation resistance and biodegradation resistance, so that the waste water is difficult to treat by the conventional method.
Most of dye production is intermittent operation, the process is laggard, the produced waste water has large fluctuation, and the water quality fluctuation of rural enterprises is more obvious.
Dye intermediates, also known as intermediates, broadly refer to various aromatic hydrocarbon derivatives used in the production of dyes and organic pigments. They are prepared by using aromatic hydrocarbons such as benzene, toluene, naphthalene and anthracene from coal chemical industry and petrochemical industry as basic raw materials through a series of organic synthesis unit processes. The variety of the dye intermediates is many, and the important ones are hundreds. Early most important dye intermediates, such as nitrobenzene, aniline, phenol, chlorobenzene, phthalic anhydride and the like, have been developed into important basic organic intermediates due to wide application and large use amount, and the annual output of the world is more than million tons. The most important dye intermediates at present are o-nitrooxybenzene, p-nitrochlorobenzene, o-nitrotoluene, p-nitrotoluene, 2-naphthol, anthraquinone, 1-aminoanthracene and the like. Starting from the intermediate, the intermediate can be prepared into various intermediates with complex structures through a series of product machine synthesis unit processes.
The dye intermediate mainly comprises four main classes of benzene intermediate, toluene intermediate, naphthalene intermediate and anthraquinone intermediate, and also comprises some heterocyclic intermediates, and the reaction processes commonly used for producing the intermediates mainly comprise nitration, sulfonation, halogenation, reduction, ammoniation, hydrolysis, oxidation, condensation and the like. The synthesis of an intermediate with a complex structure usually needs a plurality of unit processes, and different basic materials and different synthetic routes can be adopted sometimes. The dye intermediate production wastewater has the characteristics of large water quantity, high salinity, high organic matter concentration, high chromaticity and the like, and is a main environmental problem in the dye intermediate preparation industry.
The existing treatment process generally adopts flocculation, micro-electrolysis and Fenton processes for treatment, but the process has two defects: firstly, a large amount of iron mud hazardous waste is generated in the treatment process, so that the subsequent treatment cost of enterprises is increased; secondly, the treatment depth is insufficient, the salt generated after the final effluent enters the evaporation desalination device and is difficult to reach the standard of industrial by-products, and the salt can only be treated as hazardous waste, so the prior process is difficult to achieve the purpose of recycling.
Disclosure of Invention
The invention aims to provide a treatment process of high-chlorine salt dye intermediate production wastewater, which is scientific and reasonable in design, continuously solves the problem of high treatment cost of enterprise wastewater, realizes the reclamation of wastewater and has higher economic benefit; meanwhile, the invention provides a processing device which is simple and convenient to operate.
The treatment process of the high chloride salt dye intermediate production wastewater comprises the following steps:
(a) adjusting the pH value of the high-chlorine salt dye intermediate production wastewater to 3.0-3.5;
(b) introducing the wastewater obtained in the step (a) into a Fenton oxidation reactor, and adding hydrogen peroxide for reaction; the retention time of the wastewater in the Fenton oxidation reactor is 0.5 to 2.0 hours, hydrogen peroxide is added, and H is controlled2O2:FeSO4The mass ratio of (A) to (B) is 1:1-1: 5.
(c) Adding coagulant aids Polyacrylamide (PAM) and liquid caustic soda into the wastewater obtained in the step (b) for primary precipitation; the adding concentration of PAM is 3-8 mg/L; precipitating for 2-4 hours.
(d) Adding ozone into the wastewater obtained in the step (c) for catalytic oxidation; the adding concentration of ozone is 80-200 mg/L, the hydraulic retention time is 30-120 minutes, and the adding mode of ozone is jet flow;
(e) carrying out electrocatalytic oxidation on the wastewater obtained in the step (d); the anode plate is a titanium coating electrode, the cathode is a titanium mesh electrode, the distance between the electrode plates is 3-10 cm, and the current density is 5-20mA/cm2(ii) a The retention time of the wastewater is 10-120 minutes;
(f) adding liquid caustic soda into the wastewater obtained in the step (e), separating mud and water, and allowing the supernatant to enter a multi-effect evaporator for evaporation and desalination; and (c) refluxing the bottom precipitate to the step (a), adding acid to dissolve the bottom precipitate, and then feeding the bottom precipitate into a Fenton oxidation reactor for recycling.
The device for treating the high-chlorine salt dye intermediate production wastewater comprises a raw water adjusting tank, a pH adjusting tank, a Fenton oxidation reactor, a primary sedimentation tank, an ozone catalytic oxidation tank, an electrocatalytic oxidation tank, a secondary sedimentation tank and a multi-effect evaporator which are sequentially connected; the secondary sedimentation tank is also connected with a ferrous iron mud pipeline and a pH adjusting tank in sequence; the multi-effect evaporator is connected with the condensate recycling device.
Preferably, the primary sedimentation tank is connected with the sludge acid dissolution tank, the ferric iron sludge pipeline and the electrocatalytic oxidation tank in sequence.
Preferably, the Fenton oxidation reactor is connected with a hydrogen peroxide storage tank.
Specifically, the invention is realized by adopting the following treatment process:
the first step is as follows: the pH is adjusted.
Adding hydrochloric acid with the concentration of 30 wt% or liquid caustic soda with the concentration of 30 wt% through a medicine adding pipeline to adjust the pH, and controlling the pH to be about 3.
The second step is that: and (4) performing Fenton catalytic oxidation.
Controlling the pH value of inlet water to be 3.0-3.5, adding hydrogen peroxide, and controlling H2O2:FeSO4The mass ratio of (1): 1.5;
the process has the following functions:
the Fenton catalytic oxidation is that under an acidic condition, hydrogen peroxide generates hydroxyl radicals with strong oxidizing property in the presence of divalent iron ions and initiates more active oxygen to degrade organic matters. The mixed solution of hydrogen peroxide and ferrous ions oxidizes macromolecules into micromolecules, oxidizes the micromolecules into carbon dioxide and water, simultaneously, ferrous sulfate can be oxidized into ferric ions, a certain flocculation effect is achieved, and the ferric ions have a certain net catching effect, so that the purpose of treating water is achieved. The Fenton catalytic oxidation can effectively treat wastewater containing nitrobenzene organic matters and is used for decoloring and deodorizing the wastewater.
The catalyst in the Fenton catalytic oxidation process is added once and is recycled, so that a large amount of iron mud hazardous waste generated by conventional Fenton is avoided.
The third step: and (4) primary precipitation.
The process has the following functions:
and (3) separating mud and water, namely automatically flowing the supernatant to the next process for treatment, introducing the ferric hydroxide precipitate precipitated at the bottom into a rear-end sludge acid dissolving tank for acid adding and dissolving, and then performing reduction in an electrocatalytic oxidation process.
The fourth step: and (4) carrying out catalytic oxidation by ozone.
The process has the following functions:
(1) ozone is used for carrying out oxidative decomposition on organic matters in water under the catalytic action of residual iron ions in the water, so that the content of COD in the wastewater is reduced.
(2) Reducing the chroma of the waste water.
(3) The dissolved oxygen concentration of the wastewater is increased, which is beneficial to the generation of a large amount of hydrogen peroxide by the rear-end electro-catalytic cathode.
The fifth step: electrocatalytic oxidation.
The process has the following functions:
(1) hydrogen peroxide is produced near the cathode by utilizing a large amount of oxygen dissolved in water in the ozone process section to further oxidize the wastewater (the premise that hydrogen peroxide is generated at the cathode in the electrolysis process is that a large amount of dissolved oxygen exists in the water);
(2) under the action of a direct current electric field, oxidizing carbon dioxide and water by organic matters in the wastewater by utilizing the catalytic action of a titanium coating electrode, and further reducing the content of the organic matters in the wastewater;
(3) the method comprises the following steps of (1) oxidizing chloride ions in the wastewater into chlorine by utilizing an electrocatalysis effect, dissolving the chlorine in water to generate hypochlorous acid, and oxidizing ammonia nitrogen in the wastewater into nitrogen by the hypochlorous acid, so that the content of nitride in the wastewater is reduced;
(4) the electrolysis accelerates the decomposition of residual ozone in the wastewater to form the synergistic oxidation effect of the electrolytic ozone, and organic matters in the wastewater are removed to a greater extent.
(5) And reducing the ferric iron generated by the acid dissolving tank into ferrous iron by utilizing the reduction action of the cathode.
And a sixth step: and (5) secondary precipitation.
Adding liquid alkali into the electrocatalytic effluent, separating mud and water, and desalting the supernatant in a subsequent evaporator; and (4) refluxing the ferrous hydroxide precipitated at the bottom to a pH regulating tank, adding acid to dissolve the ferrous hydroxide, and then feeding the ferrous hydroxide into a Fenton oxidation reactor for recycling.
The seventh step: and (4) evaporating for desalting.
And (4) adopting a triple-effect evaporator to evaporate and desalt the treated wastewater. The evaporated condensate can be directly recycled due to low content of organic matters and nitride in the waste water before evaporation, and the evaporated solid salt sodium chloride can be sold as an industrial byproduct.
The method treats the salt-containing wastewater by utilizing a Fenton catalytic oxidation, flocculation precipitation, RCO ozone catalytic oxidation, REC electrocatalytic oxidation, secondary precipitation and evaporation desalination combined process, and the steps are organically combined, so that the treatment depth of the wastewater is ensured, and the generation of secondary hazardous waste is avoided; not only solves the problem of high treatment cost of the wastewater of enterprises, but also realizes the reclamation of the wastewater, and has higher economic benefit.
Compared with the prior art, the invention has the following beneficial effects:
(1) the whole set of process carries out multi-stage oxidation treatment on the sewage, and the wastewater treatment degree is high;
(2) the whole process disclosed by the invention does not generate secondary pollution and belongs to a green environment-friendly process;
(3) the wastewater treated by the method finally becomes recycled water and byproduct industrial salt, so that the wastewater is recycled;
(4) the processing device provided by the invention is scientific and reasonable in design and convenient to operate.
Drawings
FIG. 1 is a schematic view of a treatment device for wastewater from the production of high chloride salt dye intermediates.
In the figure: 1. a raw water adjusting tank; 2. a pH adjusting tank; 3. a Fenton oxidation reactor; 4. a hydrogen peroxide storage tank; 5. a primary sedimentation tank; 6. a coagulant aid storage tank; 7. an ozone catalytic oxidation tank; 8. an ozone generator; 9. an electrocatalytic oxidation tank; 10. a secondary sedimentation tank; 11. a multi-effect evaporator; 12. a sludge acid dissolving tank; 13. a ferric iron mud pipeline; 14. ferrous mud pipeline.
Detailed Description
The invention is further illustrated by the following specific examples, which, however, are not to be construed as limiting the invention thereto.
A treatment device for high chloride dye intermediate production wastewater is characterized in that a raw water adjusting tank 1 is sequentially connected with a pH adjusting tank 2, a Fenton oxidation reactor 3, a primary sedimentation tank 5, an ozone catalytic oxidation tank 7, an electrocatalytic oxidation tank 9, a secondary sedimentation tank 10 and a multi-effect evaporator 11; the secondary sedimentation tank 10 is also connected with a ferrous iron mud pipeline 14 and a pH adjusting tank 2 in sequence; the multi-effect evaporator 11 is connected with a condensate recycling device.
The primary sedimentation tank 5 is connected with a sludge acid dissolution tank 12, a ferric iron mud pipeline 13 and an electrocatalytic oxidation tank 9 in sequence.
The Fenton oxidation reactor 3 is connected with a hydrogen peroxide storage tank 4.
The primary sedimentation tank 5 is connected with a coagulant aid storage tank 6.
The ozone catalytic oxidation tank 7 is connected with an ozone generator.
The wastewater to be treated enters a pH adjusting tank 2 from a raw water adjusting tank 1 through a pipeline, simultaneously ferrous iron generated by a rear end electro-catalytic oxidation tank 9 is precipitated and concentrated by a secondary sedimentation tank 10 and then enters the pH adjusting tank 2 through a ferrous iron backflow pipeline 14, hydrochloric acid is added to adjust the pH of the wastewater to 3.0-3.5, then the wastewater enters a Fenton oxidation reactor 3, meanwhile, hydrogen peroxide in a hydrogen peroxide storage tank 4 is pumped into the Fenton oxidation reactor 3 through a metering pump, and the stirring reaction is carried out for 0.5-2 hours; then the wastewater enters a primary sedimentation tank 5, alkali liquor is added to adjust the pH value to 7.0-8.0, and then coagulant aid PAM is pumped into a coagulant aid storage tank 6 for sedimentation reaction for 4 hours; the supernatant enters an ozone catalytic oxidation tank 7 for secondary oxidation treatment; the ferric hydroxide sludge at the bottom enters a sludge acid-dissolving tank 12, and enters an electrocatalytic oxidation tank 9 from a ferric iron sludge pipeline 13 after being dissolved by adding acid; the supernatant fluid entering the ozone catalytic oxidation tank 7 also contains a small amount of iron ions, and forms an ozone homogeneous catalytic reaction under the action of ozone provided by the ozone generator 8, so that the reaction rate of the ozone is accelerated, and the ozone is catalyzed to generate free radicals to oxidize organic matters. The ozone catalytic oxidation effluent enters an electrocatalytic oxidation tank 9, organic matters are subjected to oxidative decomposition under the action of a catalyst on the surface of an anode, and a large amount of hydrogen peroxide is generated at a cathode due to high dissolved oxygen of the wastewater after ozone, and meanwhile, a large amount of ferric iron introduced from a sludge acid dissolving tank 12 is reduced into ferrous iron at the cathode, so that a Fenton-like reaction also exists in the electrocatalytic oxidation tank 9, and the treatment depth of the wastewater is further deepened; the effluent of the electrolytic catalytic oxidation enters a secondary sedimentation tank 10, alkali is added for mud-water separation, ferrous hydroxide at the bottom flows back to a pH adjusting tank 2 through a ferrous iron mud pipeline 14, and the ferrous hydroxide is dissolved by acid and then enters a Fenton oxidation reactor 3 for recycling; the supernatant enters a multi-effect evaporator 11 for desalination treatment, and as the wastewater is oxidized for a plurality of times and the content of pollutants in the water is extremely low, the evaporation condensate can be directly recycled, and chloride in the wastewater becomes an industrial byproduct sodium chloride, thereby realizing the recycling of the wastewater.
Based on the above description, a specific embodiment will be described below by selecting typical industrial wastewater as a treatment target.
Example 1
Aniline production sewage of a certain salt chemical plant:
the water amount is 100m3The pH value is 1.7, the COD is 2000mg/L, the ammonia nitrogen is 350mg/L, the chroma is 1500 times, the total salt is 50000mg/L, and the SS is 300 mg/L.
The treatment method provided by the invention is adopted for treatment:
wastewater to be treated enters a pH adjusting tank 2 from a raw water adjusting tank 1 through a pipeline, ferrous iron generated by a rear end electro-catalytic oxidation tank 9 is precipitated and concentrated by a secondary sedimentation tank 10 and then enters the pH adjusting tank 2 through a ferrous iron backflow pipeline 14, hydrochloric acid is added to adjust the pH of the wastewater to 3.0, then the wastewater enters a Fenton oxidation reactor 3, meanwhile, hydrogen peroxide in a hydrogen peroxide storage tank 4 is pumped into the Fenton oxidation reactor 3 through a metering pump, and H is controlled2O2:FeSO4Is 1:1 (mass ratio), stirring and reacting for 2 h; then the wastewater enters a primary sedimentation tank 5, alkali liquor is added to adjust the pH value to 8.0, and then coagulant aid PAM 5ppm is pumped into a coagulant aid storage tank 6 for sedimentation reaction for 4 hours; the supernatant enters an ozone catalytic oxidation tank 7 for secondary oxidation treatment; the ferric hydroxide sludge at the bottom enters a sludge acid-dissolving tank 12, and enters an electrocatalytic oxidation tank 9 from a ferric iron sludge pipeline 13 after being dissolved by adding acid; the supernatant fluid entering the ozone catalytic oxidation tank 7 also contains a small amount of iron ions, and forms an ozone homogeneous catalytic reaction under the action of 80mg/L ozone provided by the ozone generator 8, so that the ozone is acceleratedAnd catalyzing ozone to generate free radicals to oxidize the organic matters for 30 minutes. The effluent of the ozone catalytic oxidation enters an electrocatalytic oxidation tank 9, the hydraulic retention time is 30 minutes, the anode plate is a titanium coating electrode, the cathode is a titanium mesh electrode, the distance between the electrode plates is 3 cm, and the current density is 10mA/cm2. Organic matters are oxidized and decomposed under the action of a catalyst on the surface of the anode, and because the dissolved oxygen of the wastewater is higher after ozone, a large amount of hydrogen peroxide is generated at the cathode, and meanwhile, a large amount of ferric iron introduced from the sludge acid dissolving tank 12 is reduced into ferrous iron at the cathode, so that a Fenton reaction also exists in the electrocatalytic oxidation tank 9, and the treatment depth of the wastewater is deepened; the effluent of the electrolytic catalytic oxidation enters a secondary sedimentation tank 10, alkali is added for mud-water separation, ferrous hydroxide at the bottom flows back to a pH adjusting tank 2 through a ferrous iron mud pipeline 14, and the ferrous hydroxide is dissolved by acid and then enters a Fenton oxidation reactor 3 for recycling; the supernatant enters a multi-effect evaporator 11 for desalination treatment, and as the wastewater is oxidized for multiple times and the content of pollutants in the water is extremely low, the evaporation condensate can be directly recycled, and chloride in the wastewater becomes an industrial byproduct sodium chloride.
The wastewater is treated by the method provided by the invention:
the COD of the effluent is 15mg/L, the pH is 8.0, the ammonia nitrogen is 1.5mg/L, the SS is 6mg/L, the chroma is 5 times, and the effluent is directly reused in a circulating cooling water system; salt is sold as an industrial by-product. The treatment cost of each ton of wastewater is 23 yuan.
Example 2
The daily treatment water amount of the p-nitroaniline production wastewater of a certain chemical plant is as follows: 2000 tons, CODcr: 3400mg/L, BOD: 300mg/L, color: 600 times, SS: 350mg/L, pH: 6.0-9.0, and 8% of total salt.
The treatment method provided by the invention is adopted for treatment:
wastewater to be treated enters a pH adjusting tank 2 from a raw water adjusting tank 1 through a pipeline, ferrous iron generated by a rear end electro-catalytic oxidation tank 9 is precipitated and concentrated by a secondary sedimentation tank 10 and then enters the pH adjusting tank 2 through a ferrous iron backflow pipeline 14, hydrochloric acid is added to adjust the pH of the wastewater to 3.0, then the wastewater enters a Fenton oxidation reactor 3, meanwhile, hydrogen peroxide in a hydrogen peroxide storage tank 4 is pumped into the Fenton oxidation reactor 3 through a metering pump, and the control is carried out to controlH2O2:FeSO4Is 1: 4 (mass ratio), stirring and reacting for 1 h; then the wastewater enters a primary sedimentation tank 5, alkali liquor is added to adjust the pH value to 8.0, and then coagulant aid PAM 3ppm is pumped into a coagulant aid storage tank 6 for sedimentation reaction for 4 hours; the supernatant enters an ozone catalytic oxidation tank 7 for secondary oxidation treatment; the ferric hydroxide sludge at the bottom enters a sludge acid-dissolving tank 12, and enters an electrocatalytic oxidation tank 9 from a ferric iron sludge pipeline 13 after being dissolved by adding acid; the supernatant fluid entering the ozone catalytic oxidation tank 7 also contains a small amount of iron ions, and forms an ozone homogeneous catalytic reaction under the action of 100mg/L ozone provided by the ozone generator 8, so that the reaction rate of the ozone is accelerated, and the ozone is catalyzed to generate free radicals to oxidize organic matters for 60 minutes. The effluent of the ozone catalytic oxidation enters an electrocatalytic oxidation tank 9, the hydraulic retention time is 10 minutes, the anode plate is a titanium coating electrode, the cathode is a titanium mesh electrode, the distance between the electrode plates is 5 cm, and the current density is 20mA/cm2. Organic matters are oxidized and decomposed under the action of a catalyst on the surface of the anode, and because the dissolved oxygen of the wastewater is higher after ozone, a large amount of hydrogen peroxide is generated at the cathode, and meanwhile, a large amount of ferric iron introduced from the sludge acid dissolving tank 12 is reduced into ferrous iron at the cathode, so that a Fenton reaction also exists in the electrocatalytic oxidation tank 9, and the treatment depth of the wastewater is deepened; the effluent of the electrolytic catalytic oxidation enters a secondary sedimentation tank 10, alkali is added for mud-water separation, ferrous hydroxide at the bottom flows back to a pH adjusting tank 2 through a ferrous iron mud pipeline 14, and the ferrous hydroxide is dissolved by acid and then enters a Fenton oxidation reactor 3 for recycling; the supernatant enters a multi-effect evaporator 11 for desalination treatment, and as the wastewater is oxidized for multiple times and the content of pollutants in the water is extremely low, the evaporation condensate can be directly recycled, and chloride in the wastewater becomes an industrial byproduct sodium chloride.
Discharging water after treatment:
effluent CODcr: 10mg/L, BOD: 3mg/L, SS: 5mg/L, pH: 7.5, chroma: 4 times, directly recycling the waste water into a circulating cooling water system; salt is sold as an industrial by-product. The treatment cost of each ton of wastewater is 13 yuan.
Comparative example 1
Aniline production sewage of a certain salt chemical plant:
the water amount is 100m3H, pH of 1.7, COD of 2000mg/L,the ammonia nitrogen is 350mg/L, the chroma is 1500 times, the total salt is 50000mg/L, and the SS is 300 mg/L.
The treatment is carried out using a process similar to that of the present invention (lacking the electrocatalytic section):
wastewater to be treated enters a pH adjusting tank 2 from a raw water adjusting tank 1 through a pipeline, hydrochloric acid is added to adjust the pH of the wastewater to 3.0, then the wastewater enters a Fenton oxidation reactor 3, hydrogen peroxide and ferrous sulfate solution in a hydrogen peroxide storage tank 4 are pumped into the Fenton oxidation reactor 3 through a metering pump, and H is controlled2O2:FeSO4Is 1:1 (mass ratio), stirring and reacting for 2 h; then the wastewater enters a primary sedimentation tank 5, alkali liquor is added to adjust the pH value to 8.0, and then coagulant aid PAM 5ppm is pumped into a coagulant aid storage tank 6 for sedimentation reaction for 4 hours; the supernatant enters an ozone catalytic oxidation tank 7 for secondary oxidation treatment; carrying out filter pressing on the ferric hydroxide sludge at the bottom to form hazardous waste for outsourcing treatment; the supernatant fluid entering the ozone catalytic oxidation tank 7 also contains a small amount of iron ions, and forms an ozone homogeneous catalytic reaction under the action of 80mg/L ozone provided by the ozone generator 8, so that the reaction rate of the ozone is accelerated, and the ozone is catalyzed to generate free radicals to oxidize organic matters for 30 minutes. The effluent of the ozone catalytic oxidation enters a multi-effect evaporator 11 for desalination treatment, the evaporation condensate cannot be recycled, the effluent enters a biochemical system for further treatment and discharge, and the chlorine salt in the wastewater becomes dangerous waste and needs outsourcing treatment.
After the wastewater is treated:
the COD of the effluent is 350mg/L, the pH is 8.0, the ammonia nitrogen is 50mg/L, the SS is 32mg/L, the chroma is 51 times, the effluent cannot be directly recycled, and the effluent is discharged after further treatment; iron mud and evaporated salt generated in the treatment process are hazardous waste and need outsourcing treatment, and the treatment cost of wastewater per ton is 765 yuan.
Comparative example 2
Wastewater from p-nitroaniline production in a certain chemical plant:
daily water treatment amount: 2000 tons, CODcr: 3400mg/L, BOD: 300mg/L, color: 600 times, SS: 350mg/L, pH: 6.0-9.0, and 8% of total salt.
The treatment is carried out by adopting a similar method (ozone-free catalytic section) of the invention:
conditioning of wastewater to be treated from raw waterThe pool 1 enters a pH adjusting pool 2 through a pipeline, divalent iron generated by a rear-end electro-catalytic oxidation pool 9 is concentrated by a secondary sedimentation pool sedimentation tank sedimentation 10 and then enters the pH adjusting pool 2 through a divalent iron backflow pipeline 14, hydrochloric acid is added to adjust the pH of wastewater to 3.0, then the wastewater enters a Fenton oxidation reactor 3, meanwhile, hydrogen peroxide in a hydrogen peroxide storage tank 4 is pumped into the Fenton oxidation reactor 3 through a metering pump, and H is controlled2O2:FeSO4Is 1: 4 (mass ratio), stirring and reacting for 1 h; then the wastewater enters a primary sedimentation tank 5, alkali liquor is added to adjust the pH value to 8.0, and then coagulant aid PAM 3ppm is pumped into a coagulant aid storage tank 6 for sedimentation reaction for 4 hours; the ferric hydroxide sludge at the bottom enters a sludge acid-dissolving tank 12, and enters an electrocatalytic oxidation tank 9 from a ferric iron sludge pipeline 13 after being dissolved by adding acid; the supernatant fluid enters an electrocatalytic oxidation tank 9, the hydraulic retention time is 10 minutes, the anode plate is a titanium coating electrode, the cathode is a titanium mesh electrode, the distance between the electrode plates is 5 centimeters, and the current density is 20mA/cm2. Organic matters are oxidized and decomposed under the action of a catalyst on the surface of an anode, meanwhile, a large amount of ferric iron introduced from a sludge acid dissolving tank 12 is reduced into ferrous iron at a cathode, water discharged by electrolytic catalytic oxidation enters a secondary sedimentation tank 10, alkali is added for mud-water separation, ferrous hydroxide at the bottom flows back to a pH adjusting tank 2 through a ferrous iron mud pipeline 14, and the ferrous hydroxide is dissolved by adding acid and then is recycled in a Fenton oxidation reactor 3; the supernatant enters a multi-effect evaporator 11 for desalination treatment, the evaporation condensate cannot be recycled, the supernatant enters a biochemical system for further treatment and discharge, and the chlorine salt in the wastewater becomes dangerous waste and needs outsourcing treatment.
Discharging water after treatment:
effluent CODcr: 150mg/L, BOD: 95mg/L, SS: 5mg/L, pH: 7.5, chroma: 64 times; can not be directly recycled, and needs to be further treated and then discharged; salt evaporated in the treatment process is hazardous waste and needs outsourcing treatment, and the treatment cost of each ton of wastewater is 80 yuan.
Of course, the foregoing is only a preferred embodiment of the invention and should not be taken as limiting the scope of the embodiments of the invention. The present invention is not limited to the above examples, and equivalent changes and modifications made by those skilled in the art within the spirit and scope of the present invention should be construed as being included in the scope of the present invention.
Claims (10)
1. A treatment process of wastewater from production of high chloride salt dye intermediate is characterized by comprising the following steps: the method comprises the following steps:
(a) adjusting the pH value of the wastewater generated in the production of the high-chlorine salt dye intermediate;
(b) introducing the wastewater obtained in the step (a) into a Fenton oxidation reactor, and adding hydrogen peroxide for reaction;
(c) adding coagulant aid and liquid caustic soda into the wastewater obtained in the step (b) for primary precipitation;
(d) adding ozone into the wastewater obtained in the step (c) for catalytic oxidation;
(e) carrying out electrocatalytic oxidation on the wastewater obtained in the step (d);
(f) adding liquid caustic soda into the wastewater obtained in the step (e), separating mud and water, and allowing the supernatant to enter a multi-effect evaporator for evaporation and desalination; and (c) refluxing the bottom precipitate to the step (a), adding acid to dissolve the bottom precipitate, and then feeding the bottom precipitate into a Fenton oxidation reactor for recycling.
2. The process for treating wastewater from the production of high chloride salt dye intermediate according to claim 1, wherein: in step (a), the pH is adjusted to 3.0-3.5.
3. The process for treating wastewater from the production of high chloride salt dye intermediate according to claim 1, wherein: in the step (b), the retention time of the wastewater in the Fenton oxidation reactor is 0.5-2.0 hours, hydrogen peroxide is added, and H is controlled2O2:FeSO4The mass ratio of (A) to (B) is 1:1-1: 5.
4. The process for treating wastewater from the production of high chloride salt dye intermediate according to claim 1, wherein: in the step (c), the coagulant aid is polyacrylamide, and the adding concentration of the coagulant aid is 3-8 mg/L.
5. The process for treating wastewater from the production of high chloride salt dye intermediate according to claim 1, wherein: in step (c), precipitation is carried out for 2-4 hours.
6. The process for treating wastewater from the production of high chloride salt dye intermediate according to claim 1, wherein: in the step (d), the adding concentration of ozone is 80-200 mg/L, the hydraulic retention time is 30-120 minutes, and the adding mode of ozone is jet flow.
7. The process for treating wastewater from the production of high chloride salt dye intermediate according to claim 1, wherein: in the step (e), the anode plate is a titanium coating electrode, the cathode is a titanium mesh electrode, the distance between the electrode plates is 3-10 cm, and the current density is 5-20mA/cm2(ii) a The retention time of the waste water is 10-120 minutes.
8. A treatment apparatus for wastewater from the production of high chloride salt dye intermediate according to any one of claims 1 to 7, characterized in that: the raw water adjusting tank (1) is sequentially connected with the pH adjusting tank (2), the Fenton oxidation reactor (3), the primary sedimentation tank (5), the ozone catalytic oxidation tank (7), the electrocatalytic oxidation tank (9), the secondary sedimentation tank (10) and the multi-effect evaporator (11); the secondary sedimentation tank (10) is also sequentially connected with a ferrous iron mud pipeline (14) and a pH adjusting tank (2); the multi-effect evaporator (11) is connected with a condensate recycling device.
9. The apparatus for treating wastewater from the production of high chloride salt dye intermediate according to claim 8, wherein: the primary sedimentation tank (5) is connected with the sludge acid dissolution tank (12), the ferric iron sludge pipeline (13) and the electrocatalytic oxidation tank (9) in sequence.
10. The apparatus for treating wastewater from the production of high chloride salt dye intermediate according to claim 8, wherein: the Fenton oxidation reactor (3) is connected with the hydrogen peroxide storage tank (4).
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| CN104261622A (en) * | 2014-09-29 | 2015-01-07 | 中国电建集团中南勘测设计研究院有限公司 | Fenton sewage treatment process and equipment thereof |
| CN107032537A (en) * | 2016-10-27 | 2017-08-11 | 山东龙安泰环保科技有限公司 | A kind of processing method of refuse leachate nanofiltration concentrated water |
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