CN116589148A - Advanced sewage treatment method for producing erythromycin thiocyanate - Google Patents
Advanced sewage treatment method for producing erythromycin thiocyanate Download PDFInfo
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- CN116589148A CN116589148A CN202310858236.8A CN202310858236A CN116589148A CN 116589148 A CN116589148 A CN 116589148A CN 202310858236 A CN202310858236 A CN 202310858236A CN 116589148 A CN116589148 A CN 116589148A
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- wastewater
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- erythromycin thiocyanate
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- PGNYNCTUBKSHHL-UHFFFAOYSA-N 2,3-diaminobutanedioic acid Chemical compound OC(=O)C(N)C(N)C(O)=O PGNYNCTUBKSHHL-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000010865 sewage Substances 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title abstract description 4
- 238000000034 method Methods 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 239000002351 wastewater Substances 0.000 claims description 87
- 230000001105 regulatory effect Effects 0.000 claims description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- 241000235342 Saccharomycetes Species 0.000 claims description 16
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 16
- CDOUZKKFHVEKRI-UHFFFAOYSA-N 3-bromo-n-[(prop-2-enoylamino)methyl]propanamide Chemical compound BrCCC(=O)NCNC(=O)C=C CDOUZKKFHVEKRI-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000000701 coagulant Substances 0.000 claims description 15
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 claims description 15
- 238000007254 oxidation reaction Methods 0.000 claims description 15
- OWFJMIVZYSDULZ-PXOLEDIWSA-N (4s,4ar,5s,5ar,6s,12ar)-4-(dimethylamino)-1,5,6,10,11,12a-hexahydroxy-6-methyl-3,12-dioxo-4,4a,5,5a-tetrahydrotetracene-2-carboxamide Chemical compound C1=CC=C2[C@](O)(C)[C@H]3[C@H](O)[C@H]4[C@H](N(C)C)C(=O)C(C(N)=O)=C(O)[C@@]4(O)C(=O)C3=C(O)C2=C1O OWFJMIVZYSDULZ-PXOLEDIWSA-N 0.000 claims description 14
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 13
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 13
- 239000011790 ferrous sulphate Substances 0.000 claims description 13
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 13
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 13
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- IIUZTXTZRGLYTI-UHFFFAOYSA-N Dihydrogriseofulvin Natural products COC1CC(=O)CC(C)C11C(=O)C(C(OC)=CC(OC)=C2Cl)=C2O1 IIUZTXTZRGLYTI-UHFFFAOYSA-N 0.000 claims description 11
- UXWOXTQWVMFRSE-UHFFFAOYSA-N Griseoviridin Natural products O=C1OC(C)CC=C(C(NCC=CC=CC(O)CC(O)C2)=O)SCC1NC(=O)C1=COC2=N1 UXWOXTQWVMFRSE-UHFFFAOYSA-N 0.000 claims description 11
- DDUHZTYCFQRHIY-UHFFFAOYSA-N Negwer: 6874 Natural products COC1=CC(=O)CC(C)C11C(=O)C(C(OC)=CC(OC)=C2Cl)=C2O1 DDUHZTYCFQRHIY-UHFFFAOYSA-N 0.000 claims description 11
- 229960002867 griseofulvin Drugs 0.000 claims description 11
- DDUHZTYCFQRHIY-RBHXEPJQSA-N griseofulvin Chemical compound COC1=CC(=O)C[C@@H](C)[C@@]11C(=O)C(C(OC)=CC(OC)=C2Cl)=C2O1 DDUHZTYCFQRHIY-RBHXEPJQSA-N 0.000 claims description 11
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 11
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 11
- 241000228143 Penicillium Species 0.000 claims description 10
- 150000002191 fatty alcohols Chemical class 0.000 claims description 10
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 10
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 10
- 238000004062 sedimentation Methods 0.000 claims description 10
- 239000010802 sludge Substances 0.000 claims description 10
- JJTDIRSCDLGMRU-UHFFFAOYSA-N azane;prop-2-enamide Chemical group N.NC(=O)C=C JJTDIRSCDLGMRU-UHFFFAOYSA-N 0.000 claims description 9
- 241000222120 Candida <Saccharomycetales> Species 0.000 claims description 8
- 241000320412 Ogataea angusta Species 0.000 claims description 8
- 239000000945 filler Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 229920000578 graft copolymer Polymers 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 7
- 235000017388 Geotrichum candidum Nutrition 0.000 claims description 6
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 claims description 6
- 102000016943 Muramidase Human genes 0.000 claims description 5
- 108010014251 Muramidase Proteins 0.000 claims description 5
- 108010062010 N-Acetylmuramoyl-L-alanine Amidase Proteins 0.000 claims description 5
- 241000228127 Penicillium griseofulvum Species 0.000 claims description 5
- 230000002210 biocatalytic effect Effects 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- 229960000274 lysozyme Drugs 0.000 claims description 5
- 235000010335 lysozyme Nutrition 0.000 claims description 5
- 239000004325 lysozyme Substances 0.000 claims description 5
- 230000014759 maintenance of location Effects 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 230000001954 sterilising effect Effects 0.000 claims description 5
- 238000004659 sterilization and disinfection Methods 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 241000453701 Galactomyces candidum Species 0.000 claims 2
- 238000004065 wastewater treatment Methods 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 238000002474 experimental method Methods 0.000 abstract 1
- 238000012986 modification Methods 0.000 abstract 1
- 230000004048 modification Effects 0.000 abstract 1
- 238000003672 processing method Methods 0.000 abstract 1
- 239000003814 drug Substances 0.000 description 6
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 5
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 4
- 244000168141 Geotrichum candidum Species 0.000 description 4
- 239000005011 phenolic resin Substances 0.000 description 4
- 229920001568 phenolic resin Polymers 0.000 description 4
- 229920002401 polyacrylamide Polymers 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229960000074 biopharmaceutical Drugs 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 229940088710 antibiotic agent Drugs 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- RZHBMYQXKIDANM-UHFFFAOYSA-N dioctyl butanedioate;sodium Chemical compound [Na].CCCCCCCCOC(=O)CCC(=O)OCCCCCCCC RZHBMYQXKIDANM-UHFFFAOYSA-N 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 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 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 241000235648 Pichia Species 0.000 description 1
- 229920000289 Polyquaternium Polymers 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- 241001052560 Thallis Species 0.000 description 1
- 230000015556 catabolic process Effects 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
- 238000004042 decolorization Methods 0.000 description 1
- 238000006731 degradation reaction 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
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 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
- C02F1/30—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
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
-
- 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
- C02F1/705—Reduction by metals
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
-
- 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
- C02F2101/40—Organic compounds containing sulfur
-
- 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
-
- 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
- C02F3/347—Use of yeasts or fungi
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
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)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention discloses a sewage advanced treatment method for producing erythromycin thiocyanate, and belongs to the field of wastewater treatment. The processing method comprises the following steps: pretreatment modification unit, biocatalysis reaction unit, catalysis reaction unit, etc. The reaction conditions of all the units are optimally screened, so that all the reaction units are properly and timely combined, the matched arrangement is reasonable, the treatment efficiency is high, the process stability is good, the sewage treatment efficiency is high, the COD clearance rate is higher than that of the existing process, and the sewage treatment method has the advantages of good stability, strong reproducibility, strong applicability and the like through experiments.
Description
Technical Field
The invention relates to a method for deeply treating biological medicine sewage, in particular to a method for deeply treating sewage for producing erythromycin thiocyanate.
Background
The extraction, salifying and purifying of erythromycin thiocyanate can generate high-concentration refractory organic wastewater containing a large amount of pollutants, the pollutant components in the water are more, the pollutant degradation is difficult, and if the erythromycin thiocyanate is discharged untreated, huge pollution can be caused to the nature and the ecological balance of the nature can be further destroyed.
The technology for treating organic wastewater by utilizing saccharomycetes is a novel organic wastewater treatment technology developed in recent years, and is a technology which takes one or a combination of saccharomycetes which are screened from the environment and are suitable for specific wastewater as a main body, and achieves the aim of removing COD (chemical oxygen demand) of the wastewater by decomposing and utilizing organic matters in the wastewater under the condition of complete openness and aerobics. The treatment of antibiotics with sewage has been disclosed, in particular as follows:
patent application 20051013694.6 protects a wastewater treatment process for treating wastewater including water-based dispersions containing surfactants, colorants and silica, which is costly to operate and which is not effective in treating industrial wastewater.
Patent application 20071013952.2 discloses a clean production method of antibiotics, which comprises the steps of fermentation liquor dilution and pretreatment, filtration, decolorization, alkalization crystallization, secondary filtration and the like.
Disclosure of Invention
Aiming at the problems in the prior art, a method for deeply treating the antibiotic drug sewage of erythromycin thiocyanate provides a method for treating the biological drug pharmaceutical wastewater, which can remove hyphae and thalli and thoroughly remove organic solvents and hormone substances in the wastewater.
Specifically, the technical scheme of the invention is realized as follows:
the method for deeply treating the sewage of erythromycin thiocyanate is characterized by comprising the following steps of:
(1) Erythromycin thiocyanate wastewater pretreatment: regulating the pH value of the waste water of erythromycin thiocyanate, and adding 0.06mg/L lysozyme into the waste water to break the wall for 2 hours; adding coagulant of dioctyl sodium sulfosuccinate, higher fatty alcohol polyoxyethylene ether, polyquaternary ammonium salt acrylamide grafted copolymer, polysilicate ferric sulfate and polysilicate aluminum salt; filtering to remove precipitate;
(2) Biocatalytic reaction unit: the wastewater obtained in the step (1) enters an aerobic activated sludge tank, the pH value of the wastewater is regulated to 7.0 by using 45% sodium hydroxide, dissolved oxygen is 2mg/L, saccharomycetes are put into the aerobic activated sludge tank for biological enhancement, the reaction time is 4 hours, then Penicillium griseofulvum and medamycin are added, and effluent enters the next unit;
(3) Catalytic reduction reaction unit: regulating the pH value of the wastewater in the step (2) to 3.5-4.5, and adding filler Zn/Fe/C for catalytic reduction reaction, wherein Fe 2+ The mass concentration is 20mg/L;
(4) Catalytic oxidation reaction unit: adjusting the pH value of the wastewater in the step (3) to 3.5-4.5, adding dioctyl sodium sulfosuccinate and octadecyl trimethyl ammonium chloride for treatment for 4 hours, and then adding hydrogen peroxide, manganese dioxide and ferrous sulfate for oxidation, wherein the oxidation reaction time is 5 hours;
(5) Physical precipitation: and (3) regulating the pH value to 7, then, introducing the wastewater into a biological aerated filter, dissolving oxygen to 3.5mg/L, and discharging after the wastewater is detected to reach the standard, wherein the retention time of ultraviolet sterilization wastewater is 48 hours.
The coagulant in the step (1) is dioctyl sodium sulfosuccinate, higher fatty alcohol polyoxyethylene ether, polyquaternary ammonium salt acrylamide graft copolymer, polysilicate ferric sulfate and polysilicate aluminum salt, wherein the weight ratio of the dioctyl sodium sulfosuccinate to the higher fatty alcohol polyoxyethylene ether to the polyquaternary ammonium salt acrylamide graft copolymer to the polysilicate ferric sulfate to the polysilicate aluminum salt is 18:5:4.5:3:0.5. The coagulant dosage is 2-4 per mill, and the sedimentation time is 2 hours.
The type and the amount of the yeast in the step (2) are Hansenula polymorpha, candida and geotrichum candidum in a ratio of 10:3:1. The volume ratio of the total weight of the saccharomycetes, the penicillium griseofulvin and the medamycin to the wastewater in the step (2) is 0.8 per mill; the dosage ratio of the saccharomycete, the penicillium griseofulvin and the medamycin is 17:3.3:1.6.
The weight ratio of Zn/Fe/C in the step (3) is 40-50:12:1.
Further, the invention relates to a method for deeply treating biological medicine sewage, which comprises the following steps:
(1) Erythromycin thiocyanate wastewater pretreatment: regulating the pH value of the waste water of erythromycin thiocyanate to be neutral, and adding 0.06mg/L lysozyme into the waste water to perform wall breaking treatment for 2 hours; adding coagulant with the total weight of 2-4 per mill of sewage to settle for 2 hours; filtering to remove precipitate, wherein the coagulant is selected from dioctyl sodium sulfosuccinate, higher fatty alcohol polyoxyethylene ether, polyquaternary ammonium salt acrylamide graft copolymer, polysilicate ferric sulfate and polysilicate aluminum salt, and the weight ratio is 18:5:4.5:3:0.5;
(2) Biocatalytic reaction unit: the wastewater obtained in the step (1) enters an aerobic activated sludge tank, the pH value of the wastewater is regulated to 7.0 by using 45% sodium hydroxide, dissolved oxygen is 2mg/L, hansenula polymorpha, candida and geotrichum candidum with the weight ratio of 10:3:1 are added into the aerobic activated sludge tank for biological enhancement after 2 hours of precipitation, the reaction time is 4 hours, penicillium griseofulvum and medamycin are added, and effluent enters a secondary sedimentation tank for sedimentation for 2 hours;
(3) Catalytic reduction reaction unit: adjusting the pH value of the wastewater to 4.0, adding filler Zn/Fe/C for catalytic reduction reaction, wherein the weight ratio of Zn/Fe/C is 40-50:12:1, and Fe is 2+ The mass concentration is 20mg/L;
(4) Catalytic oxidation reaction unit: adjusting the pH value of the wastewater to 3.5, adding 0.5mg/L dioctyl sodium sulfosuccinate and 0.5mg/L octadecyl trimethyl ammonium chloride for treatment for 4 hours, adding hydrogen peroxide, manganese dioxide and ferrous sulfate into the wastewater for oxidation, wherein the oxidation reaction time is 5 hours, the mass concentration of the hydrogen peroxide is 170mg/L, the concentration of the manganese dioxide is 12mg/L, and the addition amount of the ferrous sulfate is 1.2g/L;
(5) Physical precipitation: and (3) regulating the pH value to 7, then, introducing the wastewater into a biological aerated filter, dissolving oxygen to 3.5mg/L, and discharging after the wastewater is detected to reach the standard, wherein the retention time of ultraviolet sterilization wastewater is 48 hours.
The coagulant and the treatment units are used for deeply treating the biological medicine wastewater, the biological medicine deep treatment method provided by the embodiment of the invention has a very strong treatment effect on pharmaceutical wastewater, especially erythromycin thiocyanate wastewater, and the treated wastewater meets the wastewater discharge standard. According to the technical scheme for treating the biopharmaceutical wastewater, the COD clearance rate is high, and the running cost of the biopharmaceutical wastewater is reduced.
Detailed Description
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 those skilled in the art will recognize that the present invention is not limited to these examples.
Example 1: a sewage advanced treatment method of erythromycin thiocyanate comprises the following steps:
(1) Erythromycin thiocyanate wastewater pretreatment: regulating the pH value of the waste water of erythromycin thiocyanate to be neutral, and adding 0.06mg/L lysozyme into the waste water to perform wall breaking treatment for 2 hours; adding coagulant (the type of coagulant is dioctyl sodium sulfosuccinate, higher fatty alcohol polyoxyethylene ether, polyquaternary ammonium salt acrylamide grafted copolymer, polysilicate ferric sulfate and polysilicate aluminum salt are combined, and the weight ratio of the coagulant to the polysilicate ferric sulfate to the polysilicate aluminum salt is 18:5:4.5:3:0.5) with the total weight of the sewage for sedimentation for 2 hours; filtering to remove precipitate;
(2) Biocatalytic reaction unit: the wastewater obtained in the step (1) enters an aerobic activated sludge tank, the pH value of the wastewater is regulated to 7.0 by using 45% sodium hydroxide, dissolved oxygen is 2mg/L, saccharomycetes (the weight ratio of Hansenula polymorpha, candida and geotrichum candidum in saccharomycetes is 10:3:1) are added after sedimentation for 2 hours, the mixture is added into the aerobic activated sludge tank for biological enhancement, the reaction time is 4 hours, then Penicillium griseofulvum and medamycin are added, and effluent enters a secondary sedimentation tank for sedimentation for 2 hours. Wherein the volume ratio of the total weight of the saccharomycetes, the penicillium griseofulvin and the medamycin to the wastewater is 0.8 per mill; the dosage ratio of the saccharomycete to the penicillium griseofulvin to the medamycin is 17:3.3:1.6;
(3) Catalytic reduction reaction unit: adjusting the pH value of the wastewater to 3.5-4.5, adding filler Zn/Fe/C for catalytic reduction reaction, wherein the weight ratio of Zn/Fe/C is 40-50:12:1, and the mass concentration of Fe2+ is 20mg/L;
(4) Catalytic oxidation reaction unit: adjusting the pH value of the wastewater to 3.5, adding 0.5mg/L dioctyl sodium sulfosuccinate and octadecyl trimethyl ammonium chloride (the dosage ratio of the dioctyl sodium sulfosuccinate to the octadecyl trimethyl ammonium chloride is 5.5:1.4), treating for 4 hours, adding hydrogen peroxide, manganese dioxide and ferrous sulfate into the wastewater for oxidation, wherein the oxidation reaction time is 5 hours, the mass concentration of the hydrogen peroxide is 170mg/L, the concentration of the manganese dioxide is 12mg/L, and the addition amount of the ferrous sulfate is 1.2g/L;
(5) Physical precipitation: and (3) regulating the pH value to 7, then, introducing the wastewater into a biological aerated filter, dissolving oxygen to 3.5mg/L, and discharging after the wastewater is detected to reach the standard, wherein the retention time of ultraviolet sterilization wastewater is 48 hours.
Example 2: a sewage advanced treatment method of erythromycin thiocyanate comprises the following steps:
the flocculant in erythromycin thiocyanate wastewater pretreatment is selected under the laboratory condition, a large antibiotic biopharmaceutical enterprise in Shandong is selected, and the generated pharmaceutical wastewater has COD (chemical oxygen demand) of the discharged water of 52800-63500mg/L, ammonia nitrogen content of 800-1100 mg/L and sulfuric acid radical content of 2500-3300mg/L. During the wastewater treatment period by adopting the scheme, enterprises produce erythromycin thiocyanate, and the specific flocculant is selected as follows:
(1) the method comprises the following steps Sodium dioctyl succinate sulfonate, phenolic resin, ferrous sulfate and polyacrylamide, wherein the weight ratio of the sodium dioctyl succinate sulfonate to the phenolic resin to the ferrous sulfate to the polyacrylamide is 18:5:4.5:3.5 in sequence;
(2) the method comprises the following steps Polymeric ferric sulfate, sodium alginate and ferrous sulfate in a weight ratio of 21:5:5 in sequence;
(3) the method comprises the following steps Phenolic resin, ferrous sulfate, polyacrylamide and polysilicate aluminum salt, wherein the weight ratio of the phenolic resin to the ferrous sulfate to the polyacrylamide to the polysilicate aluminum salt is 21:5:4.5:0.5 in sequence;
(4) the method comprises the following steps Dioctyl sodium sulfosuccinate, higher fatty alcohol polyoxyethylene ether, polyquaternium acrylamide graft copolymer, polysilicate ferric sulfate and polysilicate aluminum salt. The weight ratio of the components is 18:5:4.5:3:0.5 in turn;
example 3: a sewage advanced treatment method of erythromycin thiocyanate comprises the following steps:
the wastewater is obtained after the treatment of the formula (4) in the example 2, the COD of the wastewater is between 15300 and 23700mg/L, the ammonia nitrogen content is between 400 and 600mg/L, the sulfuric acid radical content is between 1000 and 1200mg/L, and the filling materials and the dosage ratio of the catalytic reaction unit are selected as follows:
(1) the method comprises the following steps Hansenula polymorpha and Penicillium griseofulvin weight ratio of 17:4.9;
(2) the method comprises the following steps Hansenula polymorpha, penicillium griseofulvin and medamycin in the weight ratio of 17:3.3:1.6 in turn;
(3) the method comprises the following steps Saccharomycetes (weight ratio of Hansenula polymorpha and candida is 10:4) of penicillium griseofulvin and medamycin, wherein the weight ratio of the saccharomycetes to the candida griseofulvin and the medamycin is 17:3.3:1.6 in sequence;
(4) the method comprises the following steps Saccharomycetes (weight ratio of Hansenula, candida and geotrichum candidum is 10:3:1), penicillium griseofulvin and medamycin are used in a weight ratio of 17:3.3:1.6;
example 4: a sewage advanced treatment method of erythromycin thiocyanate comprises the following steps:
the wastewater is obtained after the treatment of the formula (4) in the example 3, the COD of the wastewater is between 2100 and 4400mg/L, the ammonia nitrogen content is between 200 and 300mg/L, the sulfuric acid radical content is between 400 and 800mg/L, and the biocatalysis reaction unit is screened as follows:
(1) the filler Fe undergoes catalytic reduction reaction, wherein Fe 2+ The mass concentration is 20mg/L;
(2) the filler Cu/Fe/C is subjected to catalytic reduction reaction, the weight ratio of Cu/Fe/C is 40-50:12:1, and Fe is as follows 2+ The mass concentration is 20mg/L;
(3) the filler Zn/Fe/C is subjected to catalytic reduction reaction, the weight ratio of Zn/Fe/C is 40-50:12:1, and Fe is as follows 2+ The mass concentration is 20mg/L;
example 5: a sewage advanced treatment method of erythromycin thiocyanate comprises the following steps:
the wastewater is obtained after the treatment of the formula (3) in the example 4, the COD of the wastewater is between 200 and 320mg/L, the ammonia nitrogen content is between 50 and 130 mg/L, and the sulfuric acid radical content is between 40 and 60mg/L;
by adopting the technical scheme of the steps (4) and (5) of the embodiment of the invention, the COD content of the finally obtained wastewater is between 18 and 23 mg/L, the ammonia nitrogen content is 15 to 24mg/L, and the sulfhydryl content is 5 to 17mg/L.
Claims (7)
1. The method for deeply treating the sewage of erythromycin thiocyanate is characterized by comprising the following steps of:
(1) Erythromycin thiocyanate wastewater pretreatment: regulating the pH value of the waste water of erythromycin thiocyanate, and adding 0.06mg/L lysozyme into the waste water to break the wall for 2 hours; adding coagulant of dioctyl sodium sulfosuccinate, higher fatty alcohol polyoxyethylene ether, polyquaternary ammonium salt acrylamide grafted copolymer, polysilicate ferric sulfate and polysilicate aluminum salt; filtering to remove precipitate;
(2) Biocatalytic reaction unit: the wastewater obtained in the step (1) enters an aerobic activated sludge tank, the pH value of the wastewater is regulated to 7.0 by using 45% sodium hydroxide, dissolved oxygen is 2mg/L, saccharomycetes are put into the aerobic activated sludge tank for biological enhancement, the reaction time is 4 hours, then Penicillium griseofulvum and medamycin are added, and effluent enters the next unit;
(3) Catalytic reduction reaction unit: regulating the pH value of the wastewater in the step (2) to 3.5-4.5, and adding filler Zn/Fe/C for catalytic reduction reaction, wherein Fe 2+ The mass concentration is 20mg/L;
(4) Catalytic oxidation reaction unit: adjusting the pH value of the wastewater in the step (3) to 3.5-4.5, adding dioctyl sodium sulfosuccinate and octadecyl trimethyl ammonium chloride for treatment for 4 hours, and then adding hydrogen peroxide, manganese dioxide and ferrous sulfate for oxidation, wherein the oxidation reaction time is 5 hours;
(5) Physical precipitation: and (3) regulating the pH value to 7, then, introducing the wastewater into a biological aerated filter, dissolving oxygen to 3.5mg/L, and discharging after the wastewater is detected to reach the standard, wherein the retention time of ultraviolet sterilization wastewater is 48 hours.
2. The method for advanced treatment of erythromycin thiocyanate wastewater according to claim 1, wherein the coagulant in the step (1) is dioctyl sodium sulfosuccinate, higher fatty alcohol polyoxyethylene ether, polyquaternary ammonium salt acrylamide graft copolymer, polysilicate ferric sulfate and polysilicate aluminum salt, and the weight ratio of the coagulant to the high fatty alcohol polyoxyethylene ether to the polyquaternary ammonium salt acrylamide graft copolymer is 18:5:4.5:3:0.5.
3. The method for the advanced treatment of erythromycin thiocyanate wastewater according to claim 1, wherein the coagulant in the step (1) is used in an amount of 2-4% per mill, and the sedimentation time is 2 hours.
4. The method for the advanced treatment of erythromycin thiocyanate wastewater according to claim 1, wherein the type and the amount of the saccharomycetes in the step (2) are 10:3:1, namely Hansenula polymorpha, candida and geotrichum candidum.
5. The method for the advanced treatment of erythromycin thiocyanate wastewater according to claim 1, wherein the volume ratio of the total weight of the saccharomycetes, the penicillium griseofulvin and the medadamycin to the wastewater in the step (2) is 0.8 per mill; the dosage ratio of the saccharomycete, the penicillium griseofulvin and the medamycin is 17:3.3:1.6.
6. The method for the advanced treatment of erythromycin thiocyanate wastewater according to claim 1, wherein the weight ratio of Zn/Fe/C in the step (3) is 40-50:12:1.
7. The method for the advanced treatment of erythromycin thiocyanate wastewater according to claim 1, wherein the method comprises the following steps:
(1) Erythromycin thiocyanate wastewater pretreatment: regulating the pH value of the waste water of erythromycin thiocyanate to be neutral, and adding 0.06mg/L lysozyme into the waste water to perform wall breaking treatment for 2 hours; adding coagulant with the total weight of 2-4 per mill of sewage to settle for 2 hours; filtering to remove precipitate, wherein the coagulant is selected from dioctyl sodium sulfosuccinate, higher fatty alcohol polyoxyethylene ether, polyquaternary ammonium salt acrylamide graft copolymer, polysilicate ferric sulfate and polysilicate aluminum salt, and the weight ratio is 18:5:4.5:3:0.5;
(2) Biocatalytic reaction unit: the wastewater obtained in the step (1) enters an aerobic activated sludge tank, the pH value of the wastewater is regulated to 7.0 by using 45% sodium hydroxide, dissolved oxygen is 2mg/L, hansenula polymorpha, candida and geotrichum candidum with the weight ratio of 10:3:1 are added into the aerobic activated sludge tank for biological enhancement after 2 hours of precipitation, the reaction time is 4 hours, penicillium griseofulvum and medamycin are added, and effluent enters a secondary sedimentation tank for sedimentation for 2 hours;
(3) Catalytic reduction reaction unit: adjusting the pH value of the wastewater to 4.0, adding filler Zn/Fe/C for catalytic reduction reaction, wherein the weight ratio of Zn/Fe/C is 40-50:12:1, and Fe is 2+ The mass concentration is 20mg/L;
(4) Catalytic oxidation reaction unit: adjusting the pH value of the wastewater to 3.5, adding 0.5mg/L dioctyl sodium sulfosuccinate and octadecyl trimethyl ammonium chloride for treatment for 4 hours, adding hydrogen peroxide, manganese dioxide and ferrous sulfate into the wastewater for oxidation, wherein the oxidation reaction time is 5 hours, the mass concentration of the hydrogen peroxide is 170mg/L, the concentration of the manganese dioxide is 12mg/L, and the addition amount of the ferrous sulfate is 1.2g/L;
(5) Physical precipitation: and (3) regulating the pH value to 7, then, introducing the wastewater into a biological aerated filter, dissolving oxygen to 3.5mg/L, and discharging after the wastewater is detected to reach the standard, wherein the retention time of ultraviolet sterilization wastewater is 48 hours.
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