CN113860670A - Advanced treatment method of antibiotic drug sewage - Google Patents
Advanced treatment method of antibiotic drug sewage Download PDFInfo
- Publication number
- CN113860670A CN113860670A CN202111334880.2A CN202111334880A CN113860670A CN 113860670 A CN113860670 A CN 113860670A CN 202111334880 A CN202111334880 A CN 202111334880A CN 113860670 A CN113860670 A CN 113860670A
- Authority
- CN
- China
- Prior art keywords
- wastewater
- hours
- reaction
- unit
- treatment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 238000011282 treatment Methods 0.000 title claims abstract description 100
- 238000000034 method Methods 0.000 title claims abstract description 54
- 239000003814 drug Substances 0.000 title claims abstract description 23
- 230000003115 biocidal effect Effects 0.000 title claims abstract description 18
- 239000010865 sewage Substances 0.000 title claims abstract description 16
- 229940079593 drug Drugs 0.000 title claims abstract description 11
- 239000002351 wastewater Substances 0.000 claims abstract description 172
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 33
- 238000001556 precipitation Methods 0.000 claims abstract description 16
- 230000004048 modification Effects 0.000 claims abstract description 6
- 238000012986 modification Methods 0.000 claims abstract description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical group O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 46
- 239000008394 flocculating agent Substances 0.000 claims description 39
- 238000007254 oxidation reaction Methods 0.000 claims description 37
- 229940078916 carbamide peroxide Drugs 0.000 claims description 36
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical group [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 36
- AQLJVWUFPCUVLO-UHFFFAOYSA-N urea hydrogen peroxide Chemical compound OO.NC(N)=O AQLJVWUFPCUVLO-UHFFFAOYSA-N 0.000 claims description 36
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 35
- 240000004808 Saccharomyces cerevisiae Species 0.000 claims description 33
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 30
- 239000011790 ferrous sulphate Substances 0.000 claims description 30
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 30
- 238000004062 sedimentation Methods 0.000 claims description 29
- 241000894006 Bacteria Species 0.000 claims description 28
- 230000003647 oxidation Effects 0.000 claims description 28
- 239000010802 sludge Substances 0.000 claims description 27
- 241000186361 Actinobacteria <class> Species 0.000 claims description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 22
- 239000001301 oxygen Substances 0.000 claims description 22
- 229910052760 oxygen Inorganic materials 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 17
- 241000222120 Candida <Saccharomycetales> Species 0.000 claims description 16
- 230000035484 reaction time Effects 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 229920002401 polyacrylamide Polymers 0.000 claims description 15
- 244000168141 Geotrichum candidum Species 0.000 claims description 14
- 235000017388 Geotrichum candidum Nutrition 0.000 claims description 14
- MSFSPUZXLOGKHJ-UHFFFAOYSA-N Muraminsaeure Natural products OC(=O)C(C)OC1C(N)C(O)OC(CO)C1O MSFSPUZXLOGKHJ-UHFFFAOYSA-N 0.000 claims description 14
- 108010013639 Peptidoglycan Proteins 0.000 claims description 14
- 239000006228 supernatant Substances 0.000 claims description 14
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 13
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 13
- 239000005011 phenolic resin Substances 0.000 claims description 13
- 229920001568 phenolic resin Polymers 0.000 claims description 13
- 235000010413 sodium alginate Nutrition 0.000 claims description 13
- 229940005550 sodium alginate Drugs 0.000 claims description 13
- 239000000661 sodium alginate Substances 0.000 claims description 13
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 11
- 238000005273 aeration Methods 0.000 claims description 9
- 230000002210 biocatalytic effect Effects 0.000 claims description 9
- 239000000945 filler Substances 0.000 claims description 9
- 230000014759 maintenance of location Effects 0.000 claims description 9
- 239000002244 precipitate Substances 0.000 claims description 9
- 241000235058 Komagataella pastoris Species 0.000 claims description 8
- 241000235648 Pichia Species 0.000 claims description 8
- 238000001514 detection method Methods 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 7
- 239000007800 oxidant agent Substances 0.000 claims description 6
- 230000001954 sterilising effect Effects 0.000 claims description 6
- 238000004659 sterilization and disinfection Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- 230000000813 microbial effect Effects 0.000 claims description 4
- 210000002421 cell wall Anatomy 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229920001732 Lignosulfonate Polymers 0.000 claims description 2
- 241000582914 Saccharomyces uvarum Species 0.000 claims description 2
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 2
- 241000223230 Trichosporon Species 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 230000003311 flocculating effect Effects 0.000 claims description 2
- 238000005189 flocculation Methods 0.000 claims description 2
- 230000016615 flocculation Effects 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 239000002068 microbial inoculum Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- PGNYNCTUBKSHHL-UHFFFAOYSA-N 2,3-diaminobutanedioic acid Chemical compound OC(=O)C(N)C(N)C(O)=O PGNYNCTUBKSHHL-UHFFFAOYSA-N 0.000 abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 18
- 238000004065 wastewater treatment Methods 0.000 abstract description 14
- 239000004098 Tetracycline Substances 0.000 abstract description 10
- 229960002180 tetracycline Drugs 0.000 abstract description 10
- 229930101283 tetracycline Natural products 0.000 abstract description 10
- 235000019364 tetracycline Nutrition 0.000 abstract description 10
- 150000003522 tetracyclines Chemical class 0.000 abstract description 10
- 229930182555 Penicillin Natural products 0.000 abstract description 9
- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 abstract description 9
- 229940049954 penicillin Drugs 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- OJMMVQQUTAEWLP-UHFFFAOYSA-N Lincomycin Natural products CN1CC(CCC)CC1C(=O)NC(C(C)O)C1C(O)C(O)C(O)C(SC)O1 OJMMVQQUTAEWLP-UHFFFAOYSA-N 0.000 abstract 1
- OJMMVQQUTAEWLP-KIDUDLJLSA-N lincomycin Chemical compound CN1C[C@H](CCC)C[C@H]1C(=O)N[C@H]([C@@H](C)O)[C@@H]1[C@H](O)[C@H](O)[C@@H](O)[C@@H](SC)O1 OJMMVQQUTAEWLP-KIDUDLJLSA-N 0.000 abstract 1
- 229960005287 lincomycin Drugs 0.000 abstract 1
- 238000003672 processing method Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 19
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 18
- 239000000126 substance Substances 0.000 description 16
- 238000000855 fermentation Methods 0.000 description 9
- 230000004151 fermentation Effects 0.000 description 9
- ULGZDMOVFRHVEP-RWJQBGPGSA-N Erythromycin Chemical compound O([C@@H]1[C@@H](C)C(=O)O[C@@H]([C@@]([C@H](O)[C@@H](C)C(=O)[C@H](C)C[C@@](C)(O)[C@H](O[C@H]2[C@@H]([C@H](C[C@@H](C)O2)N(C)C)O)[C@H]1C)(C)O)CC)[C@H]1C[C@@](C)(OC)[C@@H](O)[C@H](C)O1 ULGZDMOVFRHVEP-RWJQBGPGSA-N 0.000 description 8
- 229960000074 biopharmaceutical Drugs 0.000 description 7
- 238000006479 redox reaction Methods 0.000 description 7
- 239000012530 fluid Substances 0.000 description 5
- 241000187559 Saccharopolyspora erythraea Species 0.000 description 4
- 239000003242 anti bacterial agent Substances 0.000 description 4
- 229940088710 antibiotic agent Drugs 0.000 description 4
- 229960003276 erythromycin Drugs 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- ABVRVIZBZKUTMK-JSYANWSFSA-M potassium clavulanate Chemical compound [K+].[O-]C(=O)[C@H]1C(=C/CO)/O[C@@H]2CC(=O)N21 ABVRVIZBZKUTMK-JSYANWSFSA-M 0.000 description 4
- 241000186046 Actinomyces Species 0.000 description 3
- 241000235342 Saccharomycetes Species 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 241001544359 Polyspora Species 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000002921 fermentation waste Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000010815 organic waste Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- RXZBMPWDPOLZGW-XMRMVWPWSA-N (E)-roxithromycin Chemical compound O([C@@H]1[C@@H](C)C(=O)O[C@@H]([C@@]([C@H](O)[C@@H](C)C(=N/OCOCCOC)/[C@H](C)C[C@@](C)(O)[C@H](O[C@H]2[C@@H]([C@H](C[C@@H](C)O2)N(C)C)O)[C@H]1C)(C)O)CC)[C@H]1C[C@@](C)(OC)[C@@H](O)[C@H](C)O1 RXZBMPWDPOLZGW-XMRMVWPWSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229960004099 azithromycin Drugs 0.000 description 1
- MQTOSJVFKKJCRP-BICOPXKESA-N azithromycin Chemical compound O([C@@H]1[C@@H](C)C(=O)O[C@@H]([C@@]([C@H](O)[C@@H](C)N(C)C[C@H](C)C[C@@](C)(O)[C@H](O[C@H]2[C@@H]([C@H](C[C@@H](C)O2)N(C)C)O)[C@H]1C)(C)O)CC)[C@H]1C[C@@](C)(OC)[C@@H](O)[C@H](C)O1 MQTOSJVFKKJCRP-BICOPXKESA-N 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012769 bulk production Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229960002626 clarithromycin Drugs 0.000 description 1
- AGOYDEPGAOXOCK-KCBOHYOISA-N clarithromycin Chemical compound O([C@@H]1[C@@H](C)C(=O)O[C@@H]([C@@]([C@H](O)[C@@H](C)C(=O)[C@H](C)C[C@](C)([C@H](O[C@H]2[C@@H]([C@H](C[C@@H](C)O2)N(C)C)O)[C@H]1C)OC)(C)O)CC)[C@H]1C[C@@](C)(OC)[C@@H](O)[C@H](C)O1 AGOYDEPGAOXOCK-KCBOHYOISA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000002147 killing effect Effects 0.000 description 1
- 239000003120 macrolide antibiotic agent Substances 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- AHLBNYSZXLDEJQ-FWEHEUNISA-N orlistat Chemical compound CCCCCCCCCCC[C@H](OC(=O)[C@H](CC(C)C)NC=O)C[C@@H]1OC(=O)[C@H]1CCCCCC AHLBNYSZXLDEJQ-FWEHEUNISA-N 0.000 description 1
- 229960001243 orlistat Drugs 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 229960005224 roxithromycin Drugs 0.000 description 1
- 230000028327 secretion Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000010200 validation analysis Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/24—Treatment of water, waste water, or sewage by flotation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5263—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using natural chemical compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic 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
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/04—Disinfection
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
- C02F3/12—Activated sludge processes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
- C02F3/342—Biological treatment of water, waste water, or sewage characterised by the microorganisms used characterised by the enzymes used
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention discloses an advanced treatment method of antibiotic drug sewage, belonging to the field of wastewater treatment. The processing method comprises the following steps: the device comprises a pretreatment modification unit, a first catalytic reaction unit, a biological catalytic reaction unit and a second catalytic reaction unit, wherein the first catalytic reaction unit is a physical precipitation unit. The method is used for treating the antibiotic production wastewater such as erythromycin thiocyanate, tetracycline, lincomycin, penicillin and the like, has high operation efficiency, ensures the quality of the effluent to be safe and stable, and can realize virtuous circle and green production of water resources inside enterprises.
Description
Technical Field
The invention relates to an advanced treatment method of biological medicine sewage, in particular to a wastewater treatment method for production of erythromycin thiocyanate, penicillin and tetracycline produced in a fermentation process, and belongs to the field of wastewater treatment.
Background
The sewage of biological medicine is mainly reflected in bulk production of bulk pharmaceutical chemicals, especially in the processes of raw material proportioning, biological fermentation, preparation purification, recovery and the like of antibiotics with larger use amount at present, such as various antibiotics such as penicillin, erythromycin and the like and intermediates thereof, and the erythromycin thiocyanate belongs to macrolide antibiotics and is mainly used for synthesizing antibiotics such as azithromycin, erythromycin, roxithromycin, clarithromycin and the like. During the extraction, salification and purification processes of erythromycin thiocyanate, high-concentration refractory organic wastewater containing a large amount of pollutants is generated, the pollutant components in the water are many, the pollutants are difficult to degrade, and if the wastewater is not discharged after treatment, the wastewater can cause huge pollution to the nature and further destroy the ecological balance of the nature.
The technology for treating organic waste water by using saccharomycetes is a novel organic waste water treatment technology developed in recent years, and is a technology for removing waste water COD and realizing water quality purification by taking one or a combination of various saccharomycetes screened from the environment and suitable for specific waste water as a main body and decomposing and utilizing organic matters in the waste water by using the saccharomycetes under the completely open and aerobic conditions. The antibiotic sewage treatment has been disclosed, and the specific details are as follows:
patent application 20051013694.6 discloses a method for treating wastewater including water-based dispersions containing surfactants, colorants and silica, and other solid materials, which is costly to operate and does not perform well in treating wastewater from the antibiotic industry.
Patent application 20071013952.2 discloses a method for producing antibiotic in a clean manner, which comprises the steps of dilution and pretreatment of a fermentation solution, filtration, decolorization, alkalization crystallization, secondary filtration and the like, and the method has the disadvantages of high operation cost, complex operation and low operation efficiency for treating antibiotic industrial wastewater due to the use of membrane filtration.
Disclosure of Invention
Aiming at the problems in the prior art, the advanced treatment method of the antibiotic drug sewage provides a method for treating the biological drug pharmaceutical wastewater, which can remove hypha and thallus, COD concentration, N-containing concentration and phosphorus-containing concentration and thoroughly remove organic solvents and hormone substances in the wastewater. Is particularly suitable for deep cleaning of the biological pharmaceutical wastewater of the biological fermentation engineering for extracting the external secretion. For example, the treatment of waste antibiotic liquid such as erythromycin thiocyanate, penicillin, potassium clavulanate, etc.
Specifically, the technical scheme of the invention is realized as follows:
an advanced treatment method of antibiotic drug sewage, which comprises the following steps:
(1) a pretreatment modification unit: adjusting the pH value of the wastewater to 6.5-7.5, and adding peptidoglycan into the wastewater for wall breaking treatment for 1-3 hours; adding a flocculating agent into the wastewater for sedimentation for 1 to 3 hours; continuously stirring, filtering and removing precipitates;
(2) a catalytic reaction first unit: after the pharmaceutical wastewater in the step (1) is pretreated, the pH value is adjusted to 4.0-5.0, the dissolved oxygen is 3-5mg/L, and catalytic reduction reaction is carried out; the filler used in the catalytic reduction reaction is a composition of ferrous salt, a catalyst and an oxidant;
(3) a biocatalytic reaction unit:
the effluent of the first catalytic reaction unit enters an aerobic activated sludge tank, hydrogen peroxide is firstly added into the aerobic activated sludge tank for reaction for 1 to 3 hours, the pH of the wastewater is adjusted to be 6.5 to 7.5, the dissolved oxygen is 3 to 4mg/L, the microbial inoculum is activated and then added into the aerobic activated sludge tank for biological enhancement, and the effluent enters a secondary sedimentation tank for natural sedimentation;
(4) a redox reaction unit:
the supernatant of the secondary sedimentation tank enters a Fenton oxidation tank for oxidation, and the oxidation reaction time is 1-10 h;
(5) physical precipitation:
and (2) adding the flocculating agent obtained in the step (1) into the wastewater after the Fenton oxidation treatment for flocculation, adjusting the pH value to 6-8, then feeding the wastewater into an aeration biological filter, carrying out ultraviolet sterilization, and discharging the wastewater after the detection reaches the standard, wherein the dissolved oxygen is 3-4mg/L, the retention time of the wastewater is 20-48 h.
Furthermore, the dosage of the peptidoglycan in the step (1) of the invention is 0.01-0.05mg/L, and the wall breaking treatment is 2 hours. Against the synthesis of bacteria, especially erythromycin, a considerable sector of polyspora species is likely to be released into the water, the road space, which has an uncertain impact on the environment and on the surrounding organisms. Therefore, the peptidoglycan can be utilized to remarkably destroy the cell wall of the saccharopolyspora erythraea, so that the peptidoglycan has a certain killing effect on various bacteria such as polyspora and monad, and the influence on the environment is avoided.
Further, the flocculating agent in the step (1) is one or a combination of more of phenolic resin, naphthalene sulfonate, sodium alginate, lignosulfonate, ferrous sulfate, sulfonated humate and polyacrylamide; the dosage of the flocculating agent is 2-4 per mill, and the settling time is 2 hours.
Furthermore, the flocculating agent in the step (1) of the invention is phenolic resin, sodium alginate, ferrous sulfate and polyacrylamide, and the flocculating agent comprises the following components in percentage by weight: phenolic resin, sodium alginate, ferrous sulfate and polyacrylamide =2:0.5:2: 0.1. The selection of the flocculating agent is the process of creative experiments of the inventor, after the treatment of the treatment unit, most suspended matters and a small part of organic matters in the wastewater are removed, the COD removal rate reaches more than 35%, and part of biological inhibiting substances, such as erythromycin thiocyanate, penicillin, potassium clavulanate, tetracycline and other various antibiotics, can be removed by adsorption of most of the biological inhibiting substances.
Further, the ferrous salt in the step (2) is one or two of ferrous sulfate and ferric chloride; the catalyst is any one or more of Mn, Cu, Pt, Pb, Zn, Ni, Au and oxide composite materials.
Further, the oxidant is any one of hydrogen peroxide, carbamide peroxide, sodium hypochlorite, hydrochloric acid, sulfuric acid, ferrate or a combination thereof.
Furthermore, the ferrous salt in the step (2) is added in an amount of 0.5-1 g/L; the catalyst is manganese dioxide with the addition of 0.05-0.1 g/L; the carbamide peroxide is a carbamide peroxide solution with the concentration of 20 percent, and the addition amount of the carbamide peroxide solution is 0.5-1 mL/L. The first catalytic reaction unit can open the ring of substances which are difficult to biodegrade, have non-uniform molecular cyclization structures and relatively stable chemical properties or change the form of a chemical molecular spatial structure by adding an oxidant and carrying out hydrogenation reduction reaction, so that part or all of stable chemical substances can be effectively converted into biodegradable substances, and good conditions are provided for subsequent biological treatment. The removal rate of COD in the pharmaceutical wastewater treated by the catalytic reduction modification unit reaches 25-35%.
Further, the hydrogen peroxide in step (3) of the present invention is a 30% hydrogen peroxide solution, and the amount thereof added is 1.0 to 2.5 mL/L. In the step, possibly residual organisms in the waste liquid are removed, and residual erythromycin thiocyanate, penicillin and potassium clavulanate can be further decomposed by utilizing the strong oxidizing property of hydrogen peroxide, so that the environment-friendly degree is achieved.
Further, the feeding ratio of the microbial bacteria in the step (3) of the invention is 0.3-5 per mill, and the weight ratio of the microbial agent selected from the group consisting of yeast, bacteria and actinomycetes is =20:0.2: 0.1; wherein the yeast is selected from one or more of cerevisiae Fermentum, Saccharomyces uvarum, Hansenula, Torulopsis, Candida, Pichia pastoris, Trichosporon gossypii, and Geotrichum candidum; the yeast is selected from candida, pichia pastoris and geotrichum candidum, and the ratio of the candida, pichia pastoris and geotrichum candidum =5:2:1 by weight. The applicant finds that in the application process, different strains, even strains with different bacteria numbers of the same strain, are different in the process of carrying out the biological catalytic reaction, and the COD removal rate of the waste water by adopting the biological strain of the invention reaches 80-90%.
Further, the advanced treatment method of the biological medicine sewage comprises the following steps:
(1) a pretreatment modification unit: breaking cell wall and precipitating with flocculant
Adjusting the pH value of the wastewater to 7.0, and adding 0.03mg/L of peptidoglycan into the wastewater for wall breaking treatment for 2 hours; adding a flocculating agent of phenolic resin, sodium alginate, ferrous sulfate and polyacrylamide in a weight ratio of 2:0.5:2:0.1 into the wastewater, and settling for 2 hours; continuously stirring, filtering and removing precipitates;
(2) a catalytic reaction unit: after pharmaceutical wastewater is pretreated, the pH value of the wastewater is adjusted to 4.5 by using 90% sulfuric acid, air is blown to ensure that the dissolved oxygen in a wastewater pool is 3-5mg/L, the catalytic reaction is continued for 2 hours, the fillers used in the catalytic reduction reaction are ferrous sulfate, carbamide peroxide and manganese dioxide, and the addition amount of the ferrous sulfate is 0.7 g/L; the catalyst is manganese dioxide, and the adding amount of the manganese dioxide is 0.075 g/L; the carbamide peroxide is a 20% carbamide peroxide solution, and the addition amount of the carbamide peroxide solution is 0.75 mL/L;
(3) a biocatalytic reaction unit:
the effluent of the first unit of catalytic reaction enters an aerobic activated sludge pool, firstly hydrogen peroxide solution with the hydrogen peroxide content of 30% is added into the aerobic activated sludge pool for reaction for 2 hours, the addition amount is 1.75mL/L, 45% sodium hydroxide is used for adjusting the pH value of the wastewater to be 7.0, the dissolved oxygen is 3-4mg/L, the combination of the yeast, the bacteria and the actinomycetes is activated according to the proportion of =20:0.2:0.1 and then is added into the aerobic activated sludge pool for biological enhancement, wherein the yeast species and the use amount are Candida, Pichia pastoris and Geotrichum candidum =5:2:1, the volume ratio of the yeast, the bacteria and the actinomycetes to the wastewater is 1.5 per thousand, the reaction time is 6 hours, and the effluent enters a secondary sedimentation pool for natural sedimentation;
(4) a redox reaction unit:
the supernatant of the secondary sedimentation tank enters a Fenton oxidation tank for oxidation, the pH value of the wastewater is adjusted to 3.5, and Fe2+The mass concentration is 14mg/L, H2O2The mass concentration is 170mg/L, and the Fenton oxidation reaction time is 5 h;
(5) physical precipitation:
and (2) flocculating the wastewater after the oxidation treatment, floating air, adjusting the pH value to 7, then feeding the wastewater into an aeration biological filter, wherein the dissolved oxygen is 3.5mg/L, the retention time of the wastewater subjected to ultraviolet sterilization is 48h, simultaneously performing ultraviolet sterilization, and discharging after the wastewater reaches the standard after detection, wherein the ultraviolet wavelength range is 200 and 275nrn, the irradiation dose is 60mJ/cm2, and the irradiation contact time is 10-20 s.
Compared with the prior art, the technical scheme of the invention has the advantages that:
1) the flocculant and each treatment unit related in the invention carry out advanced treatment on the biological medicine wastewater, and the whole process shows a remarkable synergistic treatment effect. The biological medicine advanced treatment method provided by the embodiment of the invention has a strong treatment effect on erythromycin thiocyanate, orlistat, penicillin, potassium clavulanate wastewater and a combination thereof, and the treated wastewater meets the wastewater discharge standard.
2) According to the technical scheme for treating the biological pharmaceutical wastewater, the reaction units are combined properly and timely, the cooperative arrangement is reasonable, the treatment efficiency is high, the process stability is good, the broad-spectrum applicability is strong, and the synergistic treatment effect of the pharmaceutical wastewater advanced treatment is embodied. Therefore, the invention provides the application of the pharmaceutical wastewater advanced treatment method, namely the wastewater treatment method is suitable for the application of various pharmaceutical wastewater advanced treatments; the pretreatment unit, the first catalytic unit, the biological catalytic unit, the oxidation-reduction unit, the physical unit and the like are reasonably combined, the treatment efficiency is high, the COD clearance is higher than that of the prior art, and the treatment method has the advantages of good stability, strong reproducibility, strong broad-spectrum applicability and the like.
3) The oxidant adopted by the invention can crack refractory organic matters such as cyclic compounds in the wastewater to form micromolecule substances, thereby reducing the difficulty of subsequent catalytic oxidation treatment and reducing the operation cost of biological medicine wastewater.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The present invention will be further illustrated by the following specific examples in conjunction with the pharmaceutical wastewater advanced treatment process of the present invention, and it should be understood by those skilled in the art that the present invention is not limited to these examples. The invention can simplify the treatment process, reduce the investment and reduce the operation cost for the biochemical effluent of the Chinese patent medicine with lower treatment difficulty and stable water quality through a superior form; for the pharmaceutical wastewater with large water quality fluctuation of biochemical effluent such as biological pharmacy, chemical drugs, bulk drugs and the like, the process has the advantages of enough treatment flexibility and broad-spectrum adaptability, and stable and standard discharge of external drainage.
To further verify the various bacterial populations used in the present invention, a multi-condition single-factor mini-experiment was performed as follows:
(1) and (3) verifying the use of the strain: verifying the biocatalysis by using erythromycin thiocyanate fermentation waste liquid and tetracycline fermentation waste liquid, wherein the pharmaceutical wastewater of two biological pharmaceutical companies is the A/O type wastewater treatment standard, and the indexes of the wastewater entering the biocatalysis reaction are as follows: the raw water COD is 280mg/L (wastewater generated by erythromycin thiocyanate fermentation), the raw water COD is 232 mg/L (wastewater generated by tetracycline fermentation), and the treatment capacity is 500L respectively; under the condition that other index test steps are the same; the same actinomycetes, bacteria and combinations of different strains were used for the validation, wherein the combinations of yeasts are shown in table 1,
TABLE 1 COD removal rate of wastewater treated by combination of different strains
The results of the small-test on the tetracycline wastewater and the erythromycin thiocyanate wastewater show that: the COD removal rate of the combination of candida, pichia and geotrichum candidum is over 70 percent, particularly the ratio of 5:2:1, the combination of other strains is adopted, and the possibly discharged sewage can not reach the standard without adding other treatment modes. The applicant believes that the combination of the strains is probably because the strains have a synergistic effect, the production influence among the strains is small, the waste water resource can be selectively utilized, and the practical application value is generated in the practical application process.
(2) Wall breaking treatment and flocculant precipitation treatment:
pharmaceutical wastewater of a certain biopharmaceutical company in Jiangsu, the wastewater treatment type of the company is A2The method adopts the technical scheme that the method for breaking the walls comprises the following steps of (1) treating O type wastewater, wherein the COD of raw water in the wastewater is 300mg/L (wastewater generated by fermentation of erythromycin thiocyanate), the treatment capacity is 200L respectively: adjusting the pH value of the wastewater to 7.0, adding 0.03mg/L of peptidoglycan into the wastewater for wall breaking treatment, continuously stirring the wastewater for 2 hours, adding 5 per thousand of polyacrylamide serving as a flocculating agent, and finally finding that the clearance rate of COD is 30% through detection; ultrasonic treatment (power 100-2Frequency of 20-750 kHz) is added with 5 per mill of polyacrylamide as a flocculating agent, and the clearance rate of COD is finally found to be 25 percent through detection.
(3) Investigation of flocculants
Pharmaceutical wastewater of a certain biopharmaceutical company in Jiangsu, the wastewater treatment type of the company is A2The type of O is the standard of wastewater treatment, the COD of raw water is280-320 mg/L (wastewater produced by fermentation of erythromycin thiocyanate) and 230-300 mg/L (wastewater produced by fermentation of penicillin) of raw water COD, wherein the treatment capacity is respectively 500L, and the wall breaking method related by the technical scheme of the invention comprises the following steps: adjusting the pH value of the wastewater to 7.0, adding 0.03mg/L of peptidoglycan into the wastewater for wall breaking treatment, continuously stirring for 2 hours, adding a flocculating agent with the total amount of 5 per mill, and finally finding out the COD clearance through detection; the results of COD treatment of different biopharmaceutical wastewater with non-passing flocculants are shown in Table 2.
TABLE 2 COD treatment clearance
As can be seen from the above table, in the treatment of wastewater, the treatment process of pharmaceutical wastewater of penicillin and erythromycin can effectively remove antibiotic residues in the wastewater, and can clear away drug-resistant bacteria and drug-resistant genes, so that the flocculant is suitable for large-scale popularization.
Example 1: the advanced treatment method of the biological medicine sewage sequentially comprises the following steps:
the total amount of the produced pharmaceutical wastewater of a medium-sized antibiotic biopharmaceutical enterprise in Shandong is 1200m3In one day, the aerobic effluent is at COD 400-<In the implementation of the system with the discharge standard of 50mg/L, the discharge standard sometimes fails to reach the standard. The method provided by the invention can be used for producing erythromycin thiocyanate in an enterprise during the wastewater treatment period, so that the problem that the erythromycin thiocyanate cannot reach the standard can be avoided. The specific treatment process is as follows:
wall breaking treatment and flocculant precipitation treatment: adjusting the pH value of the wastewater to 7.0, adding 0.03mg/L of peptidoglycan into the wastewater for wall breaking treatment for 2 hours, and continuously stirring; adding flocculating agents of phenolic resin, sodium alginate, ferrous sulfate and polyacrylamide in a weight ratio of 2:0.5:2:0.1 into the wastewater, and settling for 2 hours, wherein the addition amount is 3 per mill of the using amount of the flocculating agents; continuously stirring, filtering and removing precipitates; most of the wastewater suspended substances and a small amount of organic matters are removed by the treatment unit, and the COD removal rate is 40 percent.
A catalytic reaction unit: after pharmaceutical wastewater is pretreated, the pH value of the wastewater is adjusted to 4.5 by using 90% sulfuric acid, air is blown to ensure that the dissolved oxygen in a wastewater pool is 3-5mg/L, the catalytic reaction is continued for 2 hours, the fillers used in the catalytic reduction reaction are ferrous sulfate, carbamide peroxide and manganese dioxide, and the addition amount of the ferrous sulfate is 0.7 g/L; the catalyst is manganese dioxide, and the adding amount of the manganese dioxide is 0.075 g/L; the carbamide peroxide is a 20% carbamide peroxide solution, and the addition amount of the carbamide peroxide solution is 0.75 mL/L; the COD removal rate was 30%.
A biocatalytic reaction unit: the effluent of the first unit of catalytic reaction enters an aerobic activated sludge tank, firstly hydrogen peroxide solution with the hydrogen peroxide content of 30% is added into the aerobic activated sludge tank, the reaction lasts for 2 hours, the addition amount is 1.75mL/L, 45% sodium hydroxide is used for adjusting the pH value of the wastewater to be 7.0, the dissolved oxygen is 3-4mg/L, the weight ratio of the combination of the yeast, the bacteria and the actinomycetes is =20:0.2:0.1, the activated wastewater is added into the aerobic activated sludge tank for biological enhancement, wherein the yeast is candida, pichia and geotrichum candidum =5:2:1 in volume ratio, the volume ratio of the yeast, the bacteria, the actinomycetes and the wastewater is 1.5 ‰, the reaction time is 6 hours, and the wastewater enters a secondary sedimentation tank for natural sedimentation for 10 hours after water discharge; the COD removal rate is 80. The activation method of the strain comprises preparing yeast, bacteria (Saccharopolyspora erythraea), and actinomycetes (Actinomyces tundifolii) into 1.5g/L solution.
A redox reaction unit: the supernatant of the secondary sedimentation tank enters a Fenton oxidation tank for oxidation, the pH value of the wastewater is adjusted to 3.5, and Fe2+The mass concentration is 14mg/L, H2O2The mass concentration is 170mg/L, and the Fenton oxidation reaction time is 5 h; the COD removal rate is 20%.
Physical precipitation: the wastewater after oxidation treatment is flocculated by the flocculating agent used by the invention, the dosage of the flocculating agent is 5 per mill, the filtered supernatant fluid is adjusted to the pH value of 7 and then enters an aeration biological filter, and the wastewater is sterilized by ultraviolet rays (the wavelength range is 200 plus 275nrn, and the irradiation dose is 60mJ/cm2) The retention time of the wastewater is 0.5-1h, and COD and NH are detected3The concentration of H is 37mg/L and 2.28mg/L respectively, and the emission reaches the standard.
Example 2: the advanced treatment method of the biological medicine sewage sequentially comprises the following steps:
the total amount of the produced pharmaceutical wastewater of a medium-sized antibiotic biopharmaceutical enterprise in Shandong is 1200m3In one day, the aerobic effluent is at COD 300-<The emission standard of 50mg/L does not reach the standard for many times in the implementation of the system. The scheme related by the invention is adopted to carry out tetracycline production by enterprises during the wastewater treatment period, so that the problem that the tetracycline cannot reach the standard is avoided. The specific treatment process is as follows:
wall breaking treatment and flocculant precipitation treatment: adjusting the pH value of the wastewater to 7.0, adding 0.01mg/L of peptidoglycan into the wastewater for wall breaking treatment, wherein the treatment time is 2 hours, and continuously stirring; adding flocculating agents of phenolic resin, sodium alginate, ferrous sulfate and polyacrylamide in a weight ratio of 2:0.5:2:0.1 into the wastewater, and settling for 2 hours, wherein the addition amount is 2 per mill of the using amount of the flocculating agents; continuously stirring, filtering and removing precipitates; most of the wastewater suspended substances and a small amount of organic matters are removed by the treatment unit, and the COD removal rate is 35 percent.
A catalytic reaction unit: after pharmaceutical wastewater is pretreated, the pH value of the wastewater is adjusted to 4.5 by using 90% sulfuric acid, air is blown to ensure that the dissolved oxygen in a wastewater pool is 3-5mg/L, the catalytic reaction is continued for 2 hours, the fillers used in the catalytic reduction reaction are ferrous sulfate, carbamide peroxide and manganese dioxide, and the addition amount of the ferrous sulfate is 0.5 g/L; the catalyst is manganese dioxide, and the addition amount of the manganese dioxide is 0.05 g/L; the carbamide peroxide is a carbamide peroxide solution with the concentration of 20 percent, and the addition amount of the carbamide peroxide solution is 0.5 mL/L; the COD removal rate is 27%.
A biocatalytic reaction unit: the effluent of the first catalytic reaction unit enters an aerobic activated sludge tank, firstly a hydrogen peroxide solution with the hydrogen peroxide content of 30% is added into the aerobic activated sludge tank, the reaction lasts for 2 hours, the addition amount is 1.75mL/L, 45% sodium hydroxide is used for adjusting the pH value of the wastewater to be 7.0, the dissolved oxygen is 3-4mg/L, the combined weight ratio of the yeast, the bacteria and the actinomycetes is =20:0.2:0.1, the activated wastewater is (the yeast, the bacteria and the actinomycetes are prepared into a solution with the concentration of 1.5 g/L) and then is added into the aerobic activated sludge tank for biological enhancement, wherein the yeast has the volume ratio of candida, pichia pastoris and geotrichum candidum =5:2:1, the volume ratio of the yeast, the bacteria and the actinomycetes to the wastewater is 0.3 thousandths, the reaction time is 6 hours, and the effluent enters a secondary sedimentation tank for natural sedimentation for 10 hours; the COD removal rate is 80 percent.
A redox reaction unit: the supernatant of the secondary sedimentation tank enters a Fenton oxidation tank for oxidation, the pH value of the wastewater is adjusted to 3.5, and Fe2+The mass concentration is 14mg/L, H2O2The mass concentration is 170mg/L, and the Fenton oxidation reaction time is 5 h; the COD removal rate is 20 percent.
Physical precipitation: the wastewater after oxidation treatment is flocculated by the flocculating agent used by the invention, the dosage of the flocculating agent is 5 per mill, the filtered supernatant fluid is adjusted to the pH value of 7 and then enters an aeration biological filter, and the wastewater is sterilized by ultraviolet rays (the wavelength range is 200 plus 275nrn, and the irradiation dose is 60mJ/cm2) The retention time of the wastewater is 0.5-1h, and COD and NH are detected3The concentration of H is 39mg/L and 2.88mg/L respectively, and the emission reaches the standard.
Example 3: the advanced treatment method of the biological medicine sewage sequentially comprises the following steps:
the total amount of the produced pharmaceutical wastewater of a medium-sized antibiotic biopharmaceutical enterprise in Shandong is 1200m3In one day, the aerobic effluent is at COD 400-<In the implementation of the system with the discharge standard of 50mg/L, the discharge standard sometimes fails to reach the standard. The method provided by the invention can be used for producing erythromycin thiocyanate in an enterprise during the wastewater treatment period, so that the problem that the erythromycin thiocyanate cannot reach the standard can be avoided. The specific treatment process is as follows:
wall breaking treatment and flocculant precipitation treatment: adjusting the pH value of the wastewater to 7.0, adding 0.05mg/L of peptidoglycan into the wastewater for wall breaking treatment, wherein the treatment time is 2 hours, and continuously stirring; adding a flocculating agent of phenolic resin, sodium alginate, ferrous sulfate and polyacrylamide with the weight ratio of 2:0.5:2:0.1 into the wastewater, and settling for 12 hours, wherein the addition amount is 4 per thousand of the flocculating agent; continuously stirring, filtering and removing precipitates; most of the wastewater suspended substances and a small amount of organic matters are removed by the treatment unit, and the COD removal rate is 35 percent.
A catalytic reaction unit: after pharmaceutical wastewater is pretreated, the pH value of the wastewater is adjusted to 4.5 by using 90% sulfuric acid, air is blown to ensure that the dissolved oxygen in a wastewater pool is 3-5mg/L, the catalytic reaction is continued for 2 hours, the fillers used in the catalytic reduction reaction are ferrous sulfate, carbamide peroxide and manganese dioxide, and the addition amount of the ferrous sulfate is 1 g/L; the catalyst is manganese dioxide, and the addition amount of the manganese dioxide is 0.1 g/L; the carbamide peroxide is a 20% carbamide peroxide solution, and the addition amount of the carbamide peroxide is 1 mL/L; the COD removal rate is 30 percent.
A biocatalytic reaction unit: the effluent of the first catalytic reaction unit enters an aerobic activated sludge tank, firstly a hydrogen peroxide solution with the hydrogen peroxide content of 30% is added into the aerobic activated sludge tank, the reaction is carried out for 2 hours, the addition amount is 2.5mL/L, 45% sodium hydroxide is used for adjusting the pH value of the wastewater to be 7.0, the dissolved oxygen is 3-4mg/L, the combined weight ratio of the yeast, the bacteria and the actinomycetes is =20:0.2:0.1, the activated wastewater is (the yeast, the bacteria and the actinomycetes are prepared into a solution with the concentration of 1.5 g/L) and then is added into the aerobic activated sludge tank for biological enhancement, wherein the yeast has the volume ratio of candida, pichia pastoris and geotrichum candidum =5:2:1, the volume ratio of the yeast, the bacteria and the actinomycetes to the wastewater is 1.5 thousandths, the reaction time is 6 hours, and the effluent enters a secondary sedimentation tank for natural sedimentation for 10 hours; the COD removal rate is 80 percent.
A redox reaction unit: the supernatant of the secondary sedimentation tank enters a Fenton oxidation tank for oxidation, the pH value of the wastewater is adjusted to 3.5, and Fe2+The mass concentration is 14mg/L, H2O2The mass concentration is 170mg/L, and the Fenton oxidation reaction time is 5 h; the COD removal rate is between 20 percent.
Physical precipitation: the wastewater after oxidation treatment is flocculated by the flocculating agent used by the invention, the dosage of the flocculating agent is 5 per mill, the filtered supernatant fluid is adjusted to the pH value of 7 and then enters an aeration biological filter, and the wastewater is sterilized by ultraviolet rays (the wavelength range is 200 plus 275nrn, and the irradiation dose is 60mJ/cm2) The retention time of the wastewater is 0.5-1h, and COD and NH are detected3The concentration of H is 40mg/L and 2.55mg/L respectively, and the emission reaches the standard.
Example 4: the advanced treatment method of the biological medicine sewage sequentially comprises the following steps:
one in ShandongA large antibiotic biological pharmacy enterprise, the total amount of the produced pharmaceutical wastewater is 8000m3Day, COD 4400-6800mg/L, triethylamine 4002-6300 mg/L in COD<In the implementation of the system with the discharge standard of 50mg/L, the discharge standard sometimes fails to reach the standard. The method provided by the invention can be used for producing erythromycin thiocyanate in an enterprise during the wastewater treatment period, so that the problem that the erythromycin thiocyanate cannot reach the standard can be avoided. The specific treatment process is as follows:
wall breaking treatment and flocculant precipitation treatment: adjusting the pH value of the wastewater to 7.0, adding 0.05mg/L of peptidoglycan into the wastewater for wall breaking treatment, wherein the treatment time is 2 hours, and continuously stirring; adding flocculating agents of phenolic resin, sodium alginate, ferrous sulfate and polyacrylamide in a weight ratio of 2:0.5:2:0.1 into the wastewater, and settling for 2 hours, wherein the addition amount is 5 per thousand of the flocculating agents; continuously stirring, filtering and removing precipitates; most of the effluent suspended substances and a small amount of organic matters are removed by the treatment unit, the removal rate of COD is 38 percent, and the removal rate of triethylamine is 24 percent.
A catalytic reaction unit: after pharmaceutical wastewater is pretreated, the pH value of the wastewater is adjusted to 4.5 by using 90% sulfuric acid, air is blown to ensure that the dissolved oxygen in a wastewater pool is 3-5mg/L, the catalytic reaction is continued for 2 hours, the fillers used in the catalytic reduction reaction are ferrous sulfate, carbamide peroxide and manganese dioxide, and the addition amount of the ferrous sulfate is 0.7 g/L; the catalyst is manganese dioxide, and the adding amount of the manganese dioxide is 0.075 g/L; the carbamide peroxide is a 20% carbamide peroxide solution, and the addition amount of the carbamide peroxide solution is 0.75 mL/L; the removal rate of COD is 28 percent and the removal rate of triethylamine is 17 percent.
A biocatalytic reaction unit: the effluent of the first unit of catalytic reaction enters an aerobic activated sludge tank, firstly hydrogen peroxide solution with the hydrogen peroxide content of 30% is added into the aerobic activated sludge tank, the reaction lasts for 2 hours, the addition amount is 1.75mL/L, 45% sodium hydroxide is used for adjusting the pH value of the wastewater to be 7.0, the dissolved oxygen is 3-4mg/L, the weight ratio of the combination of the yeast, the bacteria and the actinomycetes is =20:0.2:0.1, the activated wastewater is added into the aerobic activated sludge tank for biological enhancement, wherein the yeast is candida, pichia and geotrichum candidum =5:2:1 in volume ratio, the volume ratio of the yeast, the bacteria, the actinomycetes and the wastewater is 1.5 ‰, the reaction time is 6 hours, and the wastewater enters a secondary sedimentation tank for natural sedimentation for 10 hours after water discharge; the removal rate of COD is 83 percent and the removal rate of triethylamine is 90 percent. The activation method of the strain comprises preparing yeast, bacteria (Saccharopolyspora erythraea), and actinomycetes (Actinomyces tundifolii) into 1.5g/L solution.
A redox reaction unit: the supernatant of the secondary sedimentation tank enters a Fenton oxidation tank for oxidation, the pH value of the wastewater is adjusted to 3.5, and Fe2+The mass concentration is 14mg/L, H2O2The mass concentration is 170mg/L, and the Fenton oxidation reaction time is 5 h; the removal rate of COD is 20 percent, and the removal rate of triethylamine is 14 percent. .
Physical precipitation: the wastewater after oxidation treatment is flocculated by the flocculating agent used by the invention, the dosage of the flocculating agent is 5 per mill, the filtered supernatant fluid is adjusted to the pH value of 7 and then enters an aeration biological filter, and the wastewater is sterilized by ultraviolet rays (the wavelength range is 200 plus 275nrn, and the irradiation dose is 60mJ/cm2) The retention time of the wastewater is 0.5-1h, and COD, triethylamine and NH are detected3The concentration of H is 41mg/L, 2.68mg/L and 11.6 mg/L respectively, and the emission reaches the standard.
Example 5: the advanced treatment method of the biological medicine sewage sequentially comprises the following steps:
the total amount of the produced pharmaceutical wastewater of a small antibiotic biopharmaceutical enterprise in Shandong is 400m3Day, the COD of raw water is 8370-10480mg/L, the COD of the discharged water is between 220-280mg/L and the COD is<The emission standard of 50mg/L does not reach the standard for many times in the implementation of the system. The scheme related by the invention is adopted to carry out tetracycline production by enterprises during the wastewater treatment period, so that the problem that the tetracycline cannot reach the standard is avoided. The specific treatment process is as follows:
wall breaking treatment and flocculant precipitation treatment: adjusting the pH value of the wastewater to 7.0, adding 0.04mg/L of peptidoglycan into the wastewater for wall breaking treatment, wherein the treatment time is 2 hours, and continuously stirring; adding flocculating agents of phenolic resin, sodium alginate, ferrous sulfate and polyacrylamide in a weight ratio of 2:0.5:2:0.1 into the wastewater, and settling for 2 hours, wherein the addition amount is 3.5 per thousand of the flocculating agents; continuously stirring, filtering and removing precipitates; most of the effluent suspended substances and a small amount of organic matters are removed by the treatment unit, and the COD removal rate is 32 percent.
A catalytic reaction unit: after pharmaceutical wastewater is pretreated, the pH value of the wastewater is adjusted to 4.5 by using 90% sulfuric acid, air is blown to ensure that the dissolved oxygen in a wastewater pool is 3-5mg/L, the catalytic reaction is continued for 2 hours, the fillers used in the catalytic reduction reaction are ferrous sulfate, carbamide peroxide and manganese dioxide, and the addition amount of the ferrous sulfate is 0.7 g/L; the catalyst is manganese dioxide, and the adding amount of the manganese dioxide is 0.075 g/L; the carbamide peroxide is a 20% carbamide peroxide solution, and the addition amount of the carbamide peroxide solution is 0.75 mL/L; the COD removal rate was 23%.
A biocatalytic reaction unit: the effluent of the first unit of catalytic reaction enters an aerobic activated sludge tank, firstly hydrogen peroxide solution with the hydrogen peroxide content of 30% is added into the aerobic activated sludge tank, the reaction lasts for 2 hours, the addition amount is 1.75mL/L, 45% sodium hydroxide is used for adjusting the pH value of the wastewater to be 7.0, the dissolved oxygen is 3-4mg/L, the weight ratio of the combination of the yeast, the bacteria and the actinomycetes is =20:0.2:0.1, the activated wastewater is added into the aerobic activated sludge tank for biological enhancement, wherein the yeast is candida, pichia and geotrichum candidum =5:2:1 in volume ratio, the volume ratio of the yeast, the bacteria, the actinomycetes and the wastewater is 1.5 ‰, the reaction time is 6 hours, and the wastewater enters a secondary sedimentation tank for natural sedimentation for 10 hours after water discharge; the COD removal rate is 81 percent. The activation method of the strain comprises preparing yeast, bacteria (Saccharopolyspora erythraea), and actinomycetes (Actinomyces tundifolii) into 1.5g/L solution.
A redox reaction unit: the supernatant of the secondary sedimentation tank enters a Fenton oxidation tank for oxidation, the pH value of the wastewater is adjusted to 3.5, and Fe2+The mass concentration is 14mg/L, H2O2The mass concentration is 170mg/L, and the Fenton oxidation reaction time is 5 h; the COD removal rate is 20 percent.
Physical precipitation: the wastewater after oxidation treatment is flocculated by the flocculating agent used by the invention, the dosage of the flocculating agent is 5 per mill, the filtered supernatant fluid is adjusted to the pH value of 7 and then enters an aeration biological filter, and the wastewater is sterilized by ultraviolet rays (the wavelength range is 200 plus 275nrn, and the irradiation dose is 60mJ/cm2) The retention time of the wastewater is 0.5-1h, and COD and NH are detected3The concentration of H is 41mg/L and 2.68mg/L respectively, and the emission reaches the standard.
Claims (10)
1. The advanced treatment method of antibiotic drug sewage is characterized by comprising the following steps:
(1) a pretreatment modification unit: adjusting the pH value of the wastewater to 6.5-7.5, adding peptidoglycan into the wastewater for wall breaking treatment for 1-3 hours; adding a flocculating agent into the wastewater for sedimentation for 1 to 3 hours; continuously stirring, filtering and removing precipitates;
(2) a catalytic reaction first unit: after the pharmaceutical wastewater in the step (1) is pretreated, the pH value is adjusted to 4.0-5.0, the dissolved oxygen is 3-5mg/L, and catalytic reduction reaction is carried out; the filler used in the catalytic reduction reaction is a composition of ferrous salt, a catalyst and an oxidant;
(3) a biocatalytic reaction unit:
the effluent of the first catalytic reaction unit enters an aerobic activated sludge tank, hydrogen peroxide is firstly added into the aerobic activated sludge tank for reaction for 1 to 3 hours, the pH of the wastewater is adjusted to be 6.5 to 7.5, the dissolved oxygen is 3 to 4mg/L, the microbial inoculum is activated and then added into the aerobic activated sludge tank for biological enhancement, and the effluent enters a secondary sedimentation tank for natural sedimentation;
(4) catalytic reaction second unit:
the supernatant of the secondary sedimentation tank enters a Fenton oxidation tank for oxidation, and the oxidation reaction time is 1-10 h;
(5) a physical precipitation unit:
and (3) flocculating the wastewater after the Fenton oxidation treatment, adjusting the pH value to 6-8, then feeding the wastewater into an aeration biological filter, wherein the dissolved oxygen is 3-4mg/L, the retention time of the wastewater is 20-48h, sterilizing by ultraviolet rays, and discharging after the wastewater reaches the standard after detection.
2. The method of claim 1, wherein the peptidanase of step (1) is used in an amount of 0.01-0.05mg/L and the wall-breaking treatment is performed for 2 hours.
3. The advanced treatment method as claimed in claim 1, wherein the flocculating agent in step (1) is one or more of phenolic resin, naphthalene sulfonate, sodium alginate, lignosulfonate, ferrous sulfate, sulfonated humate and polyacrylamide; the dosage of the flocculating agent is 2-4 per mill, and the settling time is 2 hours.
4. The advanced treatment method as claimed in claim 3, wherein the flocculating agent in step (1) is phenolic resin, sodium alginate, ferrous sulfate and polyacrylamide, and the weight ratio of the phenolic resin, the sodium alginate, the ferrous sulfate and the polyacrylamide is =2:0.5:2: 0.1.
5. The advanced treatment method according to claim 1, wherein the ferrous salt in the step (2) is one or two of ferrous sulfate and ferric chloride; the catalyst is any one or more of Mn, Cu, Pt, Pb, Zn, Ni, Au and oxide composite materials; the oxidant is any one of carbamide peroxide, sodium hypochlorite, hydrochloric acid, sulfuric acid, ferrate or a combination thereof.
6. The advanced treatment method according to claim 5, wherein the ferrous salt in the step (2) is ferrous sulfate, and the addition amount is 0.5-1 g/L; the catalyst is manganese dioxide, and the addition amount is 0.05-0.1 g/L; the carbamide peroxide is a carbamide peroxide solution with the concentration of 20 percent, and the addition amount of the carbamide peroxide solution is 0.5-1 mL/L.
7. The method of claim 1, wherein the hydrogen peroxide solution of step (3) is a 30% hydrogen peroxide solution and is added in an amount of 1.0-2.5 mL/L.
8. The advanced treatment method as claimed in claim 1, wherein the feeding ratio of the microbial bacteria in the step (3) is 0.3-5% o, and the weight ratio of the microbial agent selected from yeast, bacteria and actinomycetes is =20:0.2: 0.1; wherein the yeast is selected from one or more of cerevisiae Fermentum, Saccharomyces uvarum, Hansenula, Torulopsis, Candida, Pichia pastoris, Trichosporon gossypii, and Geotrichum candidum.
9. The advanced treatment method as claimed in claim 1, wherein the yeast in step (3) is selected from candida, pichia and geotrichum candidum, and the ratio of candida, pichia and geotrichum candidum =5:2: 1.
10. The advanced treatment process according to claim 1, characterized in that the wastewater is successively passed through the following treatment units:
(1) a pretreatment modification unit: breaking cell wall and precipitating with flocculant
Adjusting the pH value of the wastewater to 7.0, and adding 0.03mg/L of peptidoglycan into the wastewater for wall breaking treatment for 2 hours; adding a flocculating agent into the wastewater in a weight ratio of 2:0.5:2: 0.1: precipitating phenolic resin, sodium alginate, ferrous sulfate and polyacrylamide for 12 hours; continuously stirring, filtering and removing precipitates;
(2) a catalytic reaction unit: after pharmaceutical wastewater is pretreated, the pH value of the wastewater is adjusted to 4.5 by using 90% sulfuric acid, air is blown to ensure that the dissolved oxygen in a wastewater pool is 3-5mg/L, the catalytic reaction is continued for 2 hours, the fillers used in the catalytic reduction reaction are ferrous sulfate, carbamide peroxide and manganese dioxide, and the addition amount of the ferrous sulfate is 0.7 g/L; the catalyst is manganese dioxide, and the adding amount of the manganese dioxide is 0.075 g/L; the carbamide peroxide is a 20% carbamide peroxide solution, and the addition amount of the carbamide peroxide solution is 0.75 mL/L;
(3) a biocatalytic reaction unit:
the effluent of the first unit of catalytic reaction enters an aerobic activated sludge pool, firstly hydrogen peroxide solution with the hydrogen peroxide content of 30% is added into the aerobic activated sludge pool for reaction for 2 hours, the addition amount is 1.75mL/L, 45% sodium hydroxide is used for adjusting the pH value of the wastewater to be 7.0, the dissolved oxygen is 3-4mg/L, the combination of the yeast, the bacteria and the actinomycetes is activated according to the proportion of =20:0.2:0.1 and then is added into the aerobic activated sludge pool for biological enhancement, wherein the yeast species and the use amount are Candida, Pichia pastoris and Geotrichum candidum =5:2:1, the volume ratio of the yeast, the bacteria and the actinomycetes to the wastewater is 1.5 per thousand, the reaction time is 6 hours, and the effluent enters a secondary sedimentation pool for natural sedimentation;
(4) catalytic reaction second unit:
the supernatant of the secondary sedimentation tank enters a Fenton oxidation tank for oxidation, the pH value of the wastewater is adjusted to 3.5, and Fe2+The mass concentration is 14mg/L, the mass concentration of H2O2 is 170mg/L, and the Fenton oxidation reaction time is 5H;
(5) physical precipitation:
and (2) adding the flocculating agent obtained in the step (1) into the wastewater after the oxidation treatment for flocculation, adjusting the pH value to 7, then feeding the wastewater into an aeration biological filter, wherein the dissolved oxygen is 3.5mg/L, the retention time of the wastewater subjected to ultraviolet sterilization is 48h, simultaneously performing ultraviolet sterilization, and discharging the wastewater after the detection reaches the standard.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111334880.2A CN113860670A (en) | 2021-11-11 | 2021-11-11 | Advanced treatment method of antibiotic drug sewage |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111334880.2A CN113860670A (en) | 2021-11-11 | 2021-11-11 | Advanced treatment method of antibiotic drug sewage |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113860670A true CN113860670A (en) | 2021-12-31 |
Family
ID=78984359
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111334880.2A Withdrawn CN113860670A (en) | 2021-11-11 | 2021-11-11 | Advanced treatment method of antibiotic drug sewage |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113860670A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115215481A (en) * | 2022-07-27 | 2022-10-21 | 兰陵首创水务有限公司 | Method for treating industrial phosphorus-containing pharmaceutical wastewater |
| CN116589148A (en) * | 2023-07-13 | 2023-08-15 | 临沂大驰水务有限公司 | Advanced sewage treatment method for producing erythromycin thiocyanate |
-
2021
- 2021-11-11 CN CN202111334880.2A patent/CN113860670A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115215481A (en) * | 2022-07-27 | 2022-10-21 | 兰陵首创水务有限公司 | Method for treating industrial phosphorus-containing pharmaceutical wastewater |
| CN116589148A (en) * | 2023-07-13 | 2023-08-15 | 临沂大驰水务有限公司 | Advanced sewage treatment method for producing erythromycin thiocyanate |
| CN116589148B (en) * | 2023-07-13 | 2023-09-22 | 临沂大驰水务有限公司 | Advanced sewage treatment method for producing erythromycin thiocyanate |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101734825B (en) | Method for treating wastewater generated by cyclohexanone ammoximation process | |
| TWI516454B (en) | Treatment for molasses spent wash and other wastewaters | |
| CN101618919A (en) | Method for processing waste water produced by caprolactam ammoximation process | |
| CN101549940B (en) | Technique of treating textile dyeing waste water | |
| CN103508637B (en) | Traditional Chinese medicine wastewater treatment system and method for treating traditional Chinese medicine wastewater | |
| CN103011526A (en) | Method for treating erythromycin thiocyanate wastewater | |
| CN113860670A (en) | Advanced treatment method of antibiotic drug sewage | |
| CN1907889A (en) | Apparatus and method of treating city domestic refuse percolation liquid by two-stage UASB+A/O technique | |
| CN109912131A (en) | A kind of high concentration hard-degraded organic waste water processing equipment with high salt and technique | |
| CN210176671U (en) | High-salt high-concentration degradation-resistant organic wastewater treatment equipment | |
| CN105330092B (en) | A kind of technique for handling transformer greasy dirt | |
| CN108439750B (en) | Method for realizing recessive growth reduction of sludge and strengthening wastewater treatment by Fenton oxidation | |
| CN113582439A (en) | Iron-carbon Fenton pretreatment method for acidic high-salt high-concentration organic wastewater | |
| CN107055963B (en) | Efficient and low-consumption advanced treatment device and treatment method for landfill leachate | |
| CN101343129B (en) | Pretreatment technique for decolorization of wastewater at middle plate of paper-making pulping | |
| CN111252961B (en) | Treatment method of garbage penetrating fluid | |
| CN108658389A (en) | A kind of processing method of high-sulfate waste water | |
| CN110627320B (en) | Wastewater treatment combined device and process based on physical-chemical-biological method | |
| CN102616997B (en) | Method for treating wastewater generated in production process of iron oxide pigment | |
| CN105152479A (en) | Modified granular active carbon coupled membrane bioreactor (MBR) and heavy metal containing wastewater treatment method | |
| CN112961124B (en) | Method for treating sewage by using microbial preparation | |
| CN105923888B (en) | A kind of method of Fenton oxidation-MBR combined depths processing antibiotic waste water | |
| CN116589148B (en) | Advanced sewage treatment method for producing erythromycin thiocyanate | |
| CN108773911B (en) | Treating agent for garbage penetrating fluid, preparation method and treatment process thereof | |
| CN113480086A (en) | Comprehensive treatment system and process for landfill leachate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20211231 |
|
| WW01 | Invention patent application withdrawn after publication |