CN111875134A - Method for advanced treatment of secondary biochemical tail water of fermented pharmaceutical wastewater - Google Patents
Method for advanced treatment of secondary biochemical tail water of fermented pharmaceutical wastewater Download PDFInfo
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- CN111875134A CN111875134A CN202010797578.XA CN202010797578A CN111875134A CN 111875134 A CN111875134 A CN 111875134A CN 202010797578 A CN202010797578 A CN 202010797578A CN 111875134 A CN111875134 A CN 111875134A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 239000002351 wastewater Substances 0.000 title claims abstract description 111
- 238000000034 method Methods 0.000 title claims abstract description 81
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 100
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 86
- 238000001471 micro-filtration Methods 0.000 claims abstract description 28
- 238000000855 fermentation Methods 0.000 claims abstract description 15
- 230000004151 fermentation Effects 0.000 claims abstract description 15
- 230000035484 reaction time Effects 0.000 claims abstract description 11
- 238000007599 discharging Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 52
- 239000002245 particle Substances 0.000 claims description 47
- 239000012528 membrane Substances 0.000 claims description 38
- 239000012028 Fenton's reagent Substances 0.000 claims description 36
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 34
- 239000003054 catalyst Substances 0.000 claims description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- 238000007254 oxidation reaction Methods 0.000 claims description 21
- 230000000844 anti-bacterial effect Effects 0.000 claims description 19
- 239000003899 bactericide agent Substances 0.000 claims description 19
- 239000000706 filtrate Substances 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 18
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical class [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 17
- 239000011780 sodium chloride Substances 0.000 claims description 17
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- 239000000284 extract Substances 0.000 claims description 16
- 230000003647 oxidation Effects 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 230000001699 photocatalysis Effects 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 230000001678 irradiating effect Effects 0.000 claims description 9
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 9
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 claims description 9
- 238000003825 pressing Methods 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000010231 banlangen Substances 0.000 claims description 8
- 239000007853 buffer solution Substances 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 8
- 235000019387 fatty acid methyl ester Nutrition 0.000 claims description 8
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 claims description 8
- XPFJYKARVSSRHE-UHFFFAOYSA-K trisodium;2-hydroxypropane-1,2,3-tricarboxylate;2-hydroxypropane-1,2,3-tricarboxylic acid Chemical compound [Na+].[Na+].[Na+].OC(=O)CC(O)(C(O)=O)CC(O)=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O XPFJYKARVSSRHE-UHFFFAOYSA-K 0.000 claims description 8
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 7
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical group Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 3
- 150000001721 carbon Chemical class 0.000 claims description 2
- MGZTXXNFBIUONY-UHFFFAOYSA-N hydrogen peroxide;iron(2+);sulfuric acid Chemical compound [Fe+2].OO.OS(O)(=O)=O MGZTXXNFBIUONY-UHFFFAOYSA-N 0.000 claims 1
- 239000011148 porous material Substances 0.000 claims 1
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- 238000004519 manufacturing process Methods 0.000 description 5
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- 238000006731 degradation reaction Methods 0.000 description 4
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- 230000033558 biomineral tissue development Effects 0.000 description 2
- 230000001112 coagulating effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
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- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 239000005802 Mancozeb Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
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- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940126534 drug product Drugs 0.000 description 1
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- 239000007788 liquid Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 150000005181 nitrobenzenes Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
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- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—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
- C02F1/34—Treatment of water, waste water, or sewage with mechanical oscillations
- C02F1/36—Treatment of water, waste water, or sewage with mechanical oscillations ultrasonic vibrations
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
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- 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
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
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- 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
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- 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
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- 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
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
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- 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
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- 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
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- 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
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- 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
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- 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
- C02F2305/10—Photocatalysts
Abstract
The invention discloses a method for advanced treatment of secondary biochemical tail water of fermented pharmaceutical wastewater, relating to the technical field of industrial wastewater advanced treatment and comprising the following steps: 1) carrying out microfiltration pretreatment on the secondary biochemical tail water of the fermented pharmaceutical wastewater; 2) introducing the effluent obtained in the step 1) into an ozone reactor, and then introducing O3‑O2The reaction time of the mixed gas is 5-30 min; 3) and (3) introducing the effluent in the step 2) into a reverse osmosis system, and discharging the reverse osmosis produced water after reaching the standard. The invention uses the ozone-reverse osmosis combined process, can effectively remove soluble organic matters in the sewage, enables the sewage discharge to meet the requirements, and simultaneously reduces the environmental risk of secondary effluent of pharmaceutical wastewater. The method has the advantages of simple equipment, simple and convenient operation, economy, reasonableness and the like, and simultaneously has high-efficiency treatment effect and high stability. Hair brushObviously overcomes the defect of poor effect of the prior art on removing organic matters in the fermentation pharmaceutical wastewater.
Description
Technical Field
The invention relates to the technical field of industrial wastewater advanced treatment, in particular to a method for advanced treatment of secondary biochemical tail water of fermented pharmaceutical wastewater.
Background
With the rapid rise of the pharmaceutical industry in China, the productivity of the pharmaceutical manufacturing industry is at the top of the world, and the pharmaceutical manufacturing industry is also the first leading point of the world, especially the export place of raw material medicines for manufacturing chemical medicines and biological medicines. The fermentation pharmaceutical technology makes full use of the growth characteristics of microorganisms, has wide market prospect and is mainly used in the current drug production. In recent years, the water environment quality of China is continuously deteriorated, underground water resources are increasingly tense, and advanced treatment and effective recycling of industrial wastewater are effective ways for solving water resource crisis. The fermentation drug products are various in types, the production process flow is complex, most drugs are produced in an intermittent manner, the water quality and the water quantity of the antibiotic wastewater are large in change, the organic matter concentration is high, the sulfate content is large, the chromaticity is large, after primary pretreatment and secondary biological treatment, secondary effluent still has the characteristics of high chromaticity, high content of soluble organic matters, high content of salt and the like, the direct discharge and recycling standard cannot be met, and the advanced treatment is urgently needed.
The advanced treatment of wastewater is an important water treatment process for ensuring that the wastewater reaches the standard and is discharged and recycled. The common advanced treatment process of pharmaceutical wastewater comprises the following steps: adsorption, membrane separation, coagulating sedimentation, and advanced oxidation. Wherein, the activated carbon in the adsorption method has high cost and is difficult to regenerate, and is easy to cause secondary pollution; the membrane separation technology has serious membrane pollution problem; in the coagulating sedimentation method, the coagulant adding amount is large, and the sludge is easy to generate secondary pollution. The degradation of soluble organic matters by the advanced oxidation method is not thorough and the mineralization rate is low. The single process is difficult to meet the requirements of the advanced treatment process of the fermentation pharmaceutical wastewater, the stable discharge standard is difficult to realize, and the advanced treatment of the fermentation pharmaceutical wastewater needs to be combined. The ozone-reverse osmosis combined process can obviously remove the organic pollutants which are difficult to biodegrade and have toxicity and the residual active medicaments in the fermented pharmaceutical wastewater. The advanced treatment process of the pharmaceutical wastewater at the present stage is still in a research and development state, and in the face of strict emission standards and shortage of water resources, the advanced treatment process of the fermented pharmaceutical wastewater with large water quality and water quantity change is researched, the process treatment effect is evaluated, and the process has a good application prospect.
Disclosure of Invention
Aiming at the technical problems, the invention provides the method for deeply treating the secondary effluent of the pharmaceutical wastewater by the ozone-reverse osmosis combined process, which has simple process and stable effect, and can efficiently decompose organic pollutants which are difficult to biodegrade and have toxicity and residual active drugs, so that the sewage treatment meets the discharge requirement.
The technical scheme of the invention is as follows: a method for advanced treatment of secondary biochemical tail water of fermented pharmaceutical wastewater comprises the following steps:
the method comprises the following steps: adding hydrochloric acid into the fermented pharmaceutical wastewater, adjusting the pH of the fermented pharmaceutical wastewater to 3-3.5, and adding iron-carbon particles with a particle size of 2-3cm into the fermented pharmaceutical wastewater at a ratio of 50g/L3The mass ratio of iron to carbon is 15: 1-28: 1, adding a catalyst into the fermented pharmaceutical wastewater according to the proportion of 20g/L, performing electromagnetic stirring for 30-50min, filtering after the electromagnetic stirring is finished, filtering by adopting a standard sieve with the meshes of 100 and 120 to obtain a filtrate, and adding a Fenton reagent into the obtained filtrate, wherein the Fenton reagent is FeCl2、H2O2、Na2C2O4Mixing the raw materials according to the mass ratio of 1:2:1, then carrying out secondary electromagnetic stirring, keeping the stirring for 30-40min, irradiating by using ultraviolet rays with the wavelength of 10-150 nm in the stirring process, wherein the irradiation intensity is 1000-;
step two: adding the secondary biochemical tail water of the fermentation pharmaceutical wastewater after the microfiltration pretreatment into an ozone reactor, and then introducing O3-O2The ozone gas inflow amount of the mixed gas is 2Lmin-1The concentration of the ozone in the inlet air is 0-25.04mgL-1min-1And introducing saturated potassium iodide KI solution at the tail end to remove residual ozone, wherein the reaction time is 5-30 min.
Step three: and (3) washing the reverse osmosis system with reverse osmosis product water for 8-10min, adding a bactericide according to the ratio of 20mg/L, introducing the effluent obtained in the step two into the reverse osmosis system, wherein the reverse osmosis time is 20-30min, detecting reverse osmosis produced water after the reverse osmosis is finished, and discharging the water after the reverse osmosis produced water reaches the standard.
Further, in the above scheme, the aperture of the filter membrane for performing microfiltration pretreatment on the secondary biochemical tail water of the fermented pharmaceutical wastewater in the step one is 0.45 μm, so that suspended matters can be effectively removed.
Furthermore, the reaction bin in the ozone reactor in the second step is made of machine glass, so that the water quality and color change during wastewater treatment can be conveniently observed.
Further, the catalyst in the step one is prepared from 1-2mm3Activated carbon particles of (2), MnO2Mixing the powder and NaCl powder according to the mass ratio of 5:2:1, and pressing into 8-10mm3Square particles, activated carbon particles adsorbing Mn2+Ions and Na+As a catalyst to promote the micro-electrolysis reaction in the wastewater.
Furthermore, an ozone aeration porous plate is additionally arranged at the bottom end of the ozone reactor in the second step and is used for cutting ozone into uniform small bubbles and then contacting the small bubbles with the wastewater to generate oxidation reaction so that the ozone is fully contacted with the wastewater.
Further, the adding amount of the Fenton reagent in the step one is 50-80mg per liter of water, and 3-5cm is added in the Fenton reagent treatment process3TiO2The particles are used as a catalyst of a photocatalytic oxidation method, the Fenton reagent decoloration rate is 100 percent, the COD removal rate is 92.3 percent, and the nitrobenzene compounds can be effectively reduced.
Further, an ultrasonic generator is added into the ozone reactor in the second step, the ultrasonic frequency is 8-10MHz, the ultrasonic radiation degradation method is that liquid generates cavitation bubbles under ultrasonic radiation, the cavitation bubbles can absorb sound energy and collapse to release energy in a very short time, and high temperature of 1900-5200K and high pressure of over 50MPa are generated in a very small space range around the cavitation bubbles. After entering cavitation bubbles, water molecules generate high-oxidation active substances through decomposition reaction, so that the degradation of organic matters is induced; in addition, water molecules on the surface of the cavitation bubbles can form supercritical water which is beneficial to improving the chemical reaction speed.
Furthermore, the reaction time in the second step is 30min, and experiments show that 30min can effectively oxidize and degrade the wastewater, improve the oxygen content in the water and does not waste time.
Further, the bactericide added in the third step consists of the following components in parts by weight: 3-5 parts of fatty acid methyl ester, 3-8 parts of folium isatidis extract, 4-9 parts of radix isatidis extract, 2-5 parts of sodium chloride, 4-7 parts of coco betaine, 5-8 parts of citric acid-sodium citrate buffer solution, 3-10 parts of ethanol and 15-20 parts of distilled water.
Further, in the above scheme, the operating pressure in the reverse osmosis system in the third step is 0.5MPa, and experiments show that the membrane flux is maximum at the operating pressure of 0.5MPa.
Further, in the scheme, the molecular weight cut-off of the reverse osmosis membrane in the reverse osmosis system in the third step is 100Da, which is beneficial to removing a large amount of soluble organic matters.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention combines ozone and reverse osmosis efficiently, can effectively treat the secondary biochemical tail water of the fermented pharmaceutical wastewater with complex components, difficult biodegradation, high salinity and high chroma, obviously improves the effluent quality, enables the sewage discharge to meet the requirements and avoids the pollution to the environment.
2. The method has the advantages of good treatment effect, more economy, simple equipment, simple and convenient operation, no pollution, high stability and the like.
3. The invention makes up the defects that the mineralization rate of the dissolved organic matters degraded by ozone is low and the dissolved organic matters are easy to cause reverse osmosis membrane pollution at present, and improves the defects of poor treatment effect and unstable operation of the dissolved organic matters in the secondary biochemical tail water of the fermented pharmaceutical wastewater in the prior art.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is a graph showing the effect of ozone dosage on removal of soluble organics in secondary biochemical tail water of fermented pharmaceutical wastewater;
FIG. 3 is a graph showing the effect of operating pressure on the flux of a secondary biochemical tail water film of fermented pharmaceutical wastewater treated by a reverse osmosis membrane;
FIG. 4 is a graph showing the effect of reaction time on the degradation of soluble organics in the secondary biochemical tail water of fermented pharmaceutical wastewater by the ozone-reverse osmosis combined process.
Detailed Description
Example 1: the embodiment is carried out by taking secondary biochemical tail water of a pharmaceutical factory in antibiotic pharmaceutical industry as an object, and the method for deeply treating the secondary biochemical tail water of the fermented pharmaceutical wastewater comprises the following steps:
the method comprises the following steps: adding hydrochloric acid into the fermented pharmaceutical wastewater, adjusting pH of the fermented pharmaceutical wastewater to 3, adding iron-carbon particles with particle size of 2cm into the fermented pharmaceutical wastewater at a ratio of 50g/L3Adding 20g/L of catalyst into the fermented pharmaceutical wastewater according to the mass ratio of iron to carbon of 15:1, wherein the catalyst is 1mm3Activated carbon particles of (2), MnO2Pressing the powder and NaCl powder into 8mm according to the mass ratio of 5:2:13Performing electromagnetic stirring on square particles for 30min, filtering after the electromagnetic stirring is finished, filtering by adopting a standard sieve of 100 meshes to obtain filtrate, and adding a Fenton reagent into the obtained filtrate, wherein the Fenton reagent is FeCl2、H2O2、Na2C2O4Mixing according to the mass ratio of 1:2:1, then carrying out secondary electromagnetic stirring, continuously stirring for 30-40min, irradiating by using ultraviolet rays with the wavelength of 10nm in the stirring process, wherein the irradiation intensity is 1000Lux, the adding amount of Fenton reagent is 50mg per liter of water, and 3cm is added in the Fenton reagent treatment process3TiO2 particles are used as a catalyst of a photocatalytic oxidation method, and after secondary stirring is finished, the secondary biochemical tail water of the fermented pharmaceutical wastewater is subjected to microfiltration pretreatment by using a filter membrane, wherein the aperture of the filter membrane subjected to microfiltration pretreatment is 0.45 mu m;
step two: adding the secondary biochemical tail water of the fermentation pharmaceutical wastewater after the microfiltration pretreatment into an ozone reactor, and then introducing O3-O2The ozone gas inflow amount of the mixed gas is 2Lmin-1The concentration of ozone in the intake air is 25.04mgL-1min-1Introducing saturated potassium iodide KI solution at the tail end to remove residual ozone for 30min, wherein the ozone reactorThe reaction bin in the step two is made of machine glass, the bottom end of the ozone reactor is additionally provided with an ozone aeration porous plate, the ozone aeration porous plate is used for cutting ozone into uniform small bubbles and then is in contact with wastewater to generate oxidation reaction, and an ultrasonic generator is added into the ozone reactor in the step two, and the ultrasonic frequency is 8 MHz.
Step three: and (2) washing the reverse osmosis system with reverse osmosis product water for 8min, adding a bactericide according to the ratio of 20mg/L, introducing the effluent obtained in the step two into the reverse osmosis system, wherein the bactericide is conventional bactericide mancozeb, the reverse osmosis time is 20min, the intercepted molecular weight of a reverse osmosis membrane in the reverse osmosis system is 100Da, the operating pressure in the reverse osmosis system is 0.5MPa, detecting reverse osmosis produced water after the reverse osmosis is finished, and discharging after the reverse osmosis produced water is detected to reach the standard.
Example 2: the embodiment is carried out by taking secondary biochemical tail water of a pharmaceutical factory in antibiotic pharmaceutical industry as an object, and the method for deeply treating the secondary biochemical tail water of the fermented pharmaceutical wastewater comprises the following steps:
the method comprises the following steps: adding hydrochloric acid into the fermented pharmaceutical wastewater, adjusting pH of the fermented pharmaceutical wastewater to 3.2, adding iron-carbon particles with particle size of 2cm into the fermented pharmaceutical wastewater at a ratio of 50g/L3The mass ratio of iron to carbon is 26: 1, adding a catalyst into the fermented pharmaceutical wastewater according to the proportion of 20g/L, wherein the catalyst is 1mm3Activated carbon particles of (2), MnO2Mixing the powder and NaCl powder according to the mass ratio of 5:2:1, and pressing into 8mm3Performing electromagnetic stirring on square particles for 40min, filtering after the electromagnetic stirring is finished, filtering by adopting a standard sieve of 100 meshes to obtain filtrate, and adding a Fenton reagent into the obtained filtrate, wherein the Fenton reagent is FeCl2、H2O2、Na2C2O4Mixing according to the mass ratio of 1:2:1, performing secondary electromagnetic stirring, continuously stirring for 35min, irradiating by using ultraviolet rays with the wavelength of 50nm in the stirring process, wherein the irradiation intensity is 1300Lux, the adding amount of the Fenton reagent is 60mg per liter of water, and adding 3cm in the Fenton reagent treatment process3TiO2The particles are used as a catalyst of a photocatalytic oxidation method, and secondary biochemical tail water of the fermented pharmaceutical wastewater is filtered after secondary stirring is finishedPerforming microfiltration pretreatment on the membrane, wherein the aperture of the microfiltration membrane subjected to the microfiltration pretreatment is 0.45 mu m;
step two: adding the secondary biochemical tail water of the fermentation pharmaceutical wastewater after the microfiltration pretreatment into an ozone reactor, and then introducing O3-O2The ozone gas inflow amount of the mixed gas is 2Lmin-1The concentration of ozone in the intake air is 25.04mgL-1min-1And introducing a saturated potassium iodide KI solution at the tail end to remove residual ozone, wherein the reaction time is 30min, a reaction bin in the ozone reactor is made of machine glass, an ozone aeration porous plate is additionally arranged at the bottom end of the ozone reactor and is used for cutting ozone into small uniform bubbles and then contacting with wastewater to generate oxidation reaction, and an ultrasonic generator is added into the ozone reactor in the second step, wherein the ultrasonic frequency is 9 MHz.
Step three: and (2) washing the reverse osmosis system with reverse osmosis product water for 10min, adding a bactericide according to the ratio of 20mg/L, and introducing the effluent obtained in the step two into the reverse osmosis system, wherein the bactericide comprises the following components in parts by weight: 3 parts of fatty acid methyl ester, 8 parts of folium isatidis extract, 9 parts of radix isatidis extract, 5 parts of sodium chloride, 7 parts of coco betaine, 8 parts of citric acid-sodium citrate buffer solution, 10 parts of ethanol and 20 parts of distilled water, wherein the reverse osmosis duration is 20min, the molecular weight cut-off of a reverse osmosis membrane in a reverse osmosis system is 100Da, the operating pressure in the reverse osmosis system is 0.5MPa, after the reverse osmosis is finished, the reverse osmosis produced water is detected, and the detected reverse osmosis produced water is discharged after reaching the standard.
Example 3: the embodiment is carried out by taking secondary biochemical tail water of a pharmaceutical factory in antibiotic pharmaceutical industry as an object, and the method for deeply treating the secondary biochemical tail water of the fermented pharmaceutical wastewater comprises the following steps:
the method comprises the following steps: adding hydrochloric acid into the fermented pharmaceutical wastewater, adjusting pH of the fermented pharmaceutical wastewater to 3.5, adding iron-carbon particles with particle size of 2cm into the fermented pharmaceutical wastewater at a ratio of 50g/L3The mass ratio of iron to carbon is 28: 1, adding a catalyst into the fermented pharmaceutical wastewater according to the proportion of 20g/L, wherein the catalyst is 1mm3Activated carbon particles of (2), MnO2Mixing the powder and NaCl powder according to the mass ratio of 5:2:1, and pressing into 8mm3Square particles, electromagnetic stirringFiltering after electromagnetic stirring for 50min, filtering with 120-mesh standard screen to obtain filtrate, adding Fenton reagent made of FeCl into the filtrate2、H2O2、Na2C2O4Mixing according to the mass ratio of 1:2:1, performing secondary electromagnetic stirring, continuously stirring for 40min, irradiating by using ultraviolet rays with the wavelength of 10nm in the stirring process, wherein the irradiation intensity is 1500Lux, the adding amount of the Fenton reagent is 80mg per liter of water, and adding 3cm in the Fenton reagent treatment process3TiO2The particles are used as a catalyst of a photocatalytic oxidation method, and after secondary stirring is finished, microfiltration pretreatment is carried out on the secondary biochemical tail water of the fermented pharmaceutical wastewater by using a filter membrane, wherein the aperture of the filter membrane subjected to microfiltration pretreatment is 0.45 mu m;
step two: adding the secondary biochemical tail water of the fermentation pharmaceutical wastewater after the microfiltration pretreatment into an ozone reactor, and then introducing O3-O2The ozone gas inflow amount of the mixed gas is 2Lmin-1The concentration of ozone in the intake air is 25.04mgL-1min-1And introducing a saturated potassium iodide KI solution at the tail end to remove residual ozone, wherein the reaction time is 30min, a reaction bin in the ozone reactor is made of machine glass, an ozone aeration porous plate is additionally arranged at the bottom end of the ozone reactor and is used for cutting ozone into small uniform bubbles and then contacting with wastewater to generate oxidation reaction, and an ultrasonic generator is added into the ozone reactor in the second step, wherein the ultrasonic frequency is 8 MHz.
Step three: and (2) washing the reverse osmosis system with reverse osmosis product water for 10min, adding a bactericide according to the ratio of 20mg/L, and introducing the effluent obtained in the step two into the reverse osmosis system, wherein the bactericide comprises the following components in parts by weight: 3 parts of fatty acid methyl ester, 8 parts of folium isatidis extract, 9 parts of radix isatidis extract, 5 parts of sodium chloride, 7 parts of coco betaine, 8 parts of citric acid-sodium citrate buffer solution, 10 parts of ethanol and 20 parts of distilled water, wherein the reverse osmosis duration is 20min, the molecular weight cut-off of a reverse osmosis membrane in a reverse osmosis system is 100Da, the operating pressure in the reverse osmosis system is 0.5MPa, after the reverse osmosis is finished, the reverse osmosis produced water is detected, and the detected reverse osmosis produced water is discharged after reaching the standard.
Example 4: the embodiment is carried out by taking secondary biochemical tail water of a pharmaceutical factory in antibiotic pharmaceutical industry as an object, and the method for deeply treating the secondary biochemical tail water of the fermented pharmaceutical wastewater comprises the following steps:
the method comprises the following steps: adding hydrochloric acid into the fermented pharmaceutical wastewater, adjusting pH of the fermented pharmaceutical wastewater to 3, adding iron-carbon particles with particle size of 3cm into the fermented pharmaceutical wastewater at a ratio of 50g/L3The mass ratio of iron to carbon is 28: 1, adding a catalyst into the fermented pharmaceutical wastewater according to the proportion of 20g/L, wherein the catalyst is 1mm3Activated carbon particles of (2), MnO2Mixing the powder and NaCl powder according to the mass ratio of 5:2:1, and pressing into 9mm3Electromagnetically stirring square particles for 50min, filtering after the electromagnetic stirring is finished, filtering by adopting a 120-mesh standard screen to obtain a filtrate, and adding a Fenton reagent into the obtained filtrate, wherein the Fenton reagent is FeCl2、H2O2、Na2C2O4Mixing according to the mass ratio of 1:2:1, performing secondary electromagnetic stirring, continuously stirring for 40min, irradiating by using ultraviolet rays with the wavelength of 100nm in the stirring process, wherein the irradiation intensity is 1500Lux, the adding amount of the Fenton reagent is 80mg per liter of water, and adding 3cm in the Fenton reagent treatment process3TiO2The particles are used as a catalyst of a photocatalytic oxidation method, and after secondary stirring is finished, microfiltration pretreatment is carried out on the secondary biochemical tail water of the fermented pharmaceutical wastewater by using a filter membrane, wherein the aperture of the filter membrane subjected to microfiltration pretreatment is 0.45 mu m;
step two: adding the secondary biochemical tail water of the fermentation pharmaceutical wastewater after the microfiltration pretreatment into an ozone reactor, and then introducing O3-O2The ozone gas inflow amount of the mixed gas is 2Lmin-1The concentration of ozone in the intake air is 10mgL-1min-1And introducing a saturated potassium iodide KI solution at the tail end to remove residual ozone, wherein the reaction time is 20min, a reaction bin in the ozone reactor is made of machine glass, an ozone aeration porous plate is additionally arranged at the bottom end of the ozone reactor and is used for cutting ozone into small uniform bubbles and then contacting with wastewater to generate oxidation reaction, and an ultrasonic generator is added into the ozone reactor in the second step, wherein the ultrasonic frequency is 9 MHz.
Step three: and (2) washing the reverse osmosis system with reverse osmosis product water for 10min, adding a bactericide according to the ratio of 20mg/L, and introducing the effluent obtained in the step two into the reverse osmosis system, wherein the bactericide comprises the following components in parts by weight: 3 parts of fatty acid methyl ester, 8 parts of folium isatidis extract, 9 parts of radix isatidis extract, 5 parts of sodium chloride, 7 parts of coco betaine, 8 parts of citric acid-sodium citrate buffer solution, 10 parts of ethanol and 20 parts of distilled water, wherein the reverse osmosis duration is 25min, the molecular weight cut-off of a reverse osmosis membrane in a reverse osmosis system is 100Da, the operating pressure in the reverse osmosis system is 0.5MPa, after the reverse osmosis is finished, the reverse osmosis produced water is detected, and the detected reverse osmosis produced water is discharged after reaching the standard.
Example 5: the embodiment is carried out by taking secondary biochemical tail water of a pharmaceutical factory in antibiotic pharmaceutical industry as an object, and the method for deeply treating the secondary biochemical tail water of the fermented pharmaceutical wastewater comprises the following steps:
the method comprises the following steps: adding hydrochloric acid into the fermented pharmaceutical wastewater, adjusting pH of the fermented pharmaceutical wastewater to 3, adding iron-carbon particles with particle size of 3cm into the fermented pharmaceutical wastewater at a ratio of 50g/L3The mass ratio of iron to carbon is 28: 1, adding a catalyst into the fermented pharmaceutical wastewater according to the proportion of 20g/L, wherein the catalyst is 1mm3Activated carbon particles of (2), MnO2Mixing the powder and NaCl powder according to the mass ratio of 5:2:1, and pressing into 9mm3Electromagnetically stirring square particles for 50min, filtering after the electromagnetic stirring is finished, filtering by adopting a 120-mesh standard screen to obtain a filtrate, and adding a Fenton reagent into the obtained filtrate, wherein the Fenton reagent is FeCl2、H2O2、Na2C2O4Mixing according to the mass ratio of 1:2:1, performing secondary electromagnetic stirring, continuously stirring for 40min, irradiating by using ultraviolet rays with the wavelength of 140nm in the stirring process, wherein the irradiation intensity is 1500Lux, the adding amount of the Fenton reagent is 80mg per liter of water, and adding 3cm in the Fenton reagent treatment process3TiO2The particles are used as a catalyst of a photocatalytic oxidation method, and after secondary stirring is finished, microfiltration pretreatment is carried out on the secondary biochemical tail water of the fermented pharmaceutical wastewater by using a filter membrane, wherein the aperture of the filter membrane subjected to microfiltration pretreatment is 0.45 mu m;
step two: will be provided withAdding the secondary biochemical tail water of the fermentation pharmaceutical wastewater after the microfiltration pretreatment into an ozone reactor, and then introducing O3-O2The ozone gas inflow amount of the mixed gas is 2Lmin-1The concentration of ozone in the intake air is 11.03mgL-1min-1And introducing a saturated potassium iodide KI solution at the tail end to remove residual ozone, wherein the reaction time is 30min, a reaction bin in the ozone reactor is made of machine glass, an ozone aeration porous plate is additionally arranged at the bottom end of the ozone reactor and is used for cutting ozone into small uniform bubbles and then contacting with wastewater to generate oxidation reaction, and an ultrasonic generator is added into the ozone reactor in the second step, and the ultrasonic frequency is 10 MHz.
Step three: and (2) washing the reverse osmosis system with reverse osmosis product water for 10min, adding a bactericide according to the ratio of 20mg/L, and introducing the effluent obtained in the step two into the reverse osmosis system, wherein the bactericide comprises the following components in parts by weight: 5 parts of fatty acid methyl ester, 8 parts of folium isatidis extract, 9 parts of radix isatidis extract, 5 parts of sodium chloride, 7 parts of coco betaine, 8 parts of citric acid-sodium citrate buffer solution, 10 parts of ethanol and 20 parts of distilled water, wherein the reverse osmosis duration is 25min, the molecular weight cut-off of a reverse osmosis membrane in a reverse osmosis system is 100Da, the operating pressure in the reverse osmosis system is 0.5MPa, after the reverse osmosis is finished, the reverse osmosis produced water is detected, and the detected reverse osmosis produced water is discharged after reaching the standard.
Example 6: the embodiment is carried out by taking secondary biochemical tail water of a pharmaceutical factory in antibiotic pharmaceutical industry as an object, and the method for deeply treating the secondary biochemical tail water of the fermented pharmaceutical wastewater comprises the following steps:
the method comprises the following steps: adding hydrochloric acid into the fermented pharmaceutical wastewater, adjusting pH of the fermented pharmaceutical wastewater to 3, adding iron-carbon particles with particle size of 3cm into the fermented pharmaceutical wastewater at a ratio of 50g/L3The mass ratio of iron to carbon is 28: 1, adding a catalyst into the fermented pharmaceutical wastewater according to the proportion of 20g/L, wherein the catalyst is 1mm3Activated carbon particles of (2), MnO2Mixing the powder and NaCl powder according to the mass ratio of 5:2:1, and pressing into 10mm3Performing electromagnetic stirring on square particles for 50min, filtering after the electromagnetic stirring is completed, filtering by adopting a 120-mesh standard screen to obtain filtrate, and performing secondary filtration on the filtrateAdding a Fenton reagent consisting of FeCl into the filtrate2、H2O2、Na2C2O4Mixing according to the mass ratio of 1:2:1, performing secondary electromagnetic stirring, continuously stirring for 40min, irradiating by using ultraviolet rays with the wavelength of 90nm in the stirring process, wherein the irradiation intensity is 1500Lux, the adding amount of the Fenton reagent is 80mg per liter of water, and adding 5cm in the Fenton reagent treatment process3TiO2The particles are used as a catalyst of a photocatalytic oxidation method, and after secondary stirring is finished, microfiltration pretreatment is carried out on the secondary biochemical tail water of the fermented pharmaceutical wastewater by using a filter membrane, wherein the aperture of the filter membrane subjected to microfiltration pretreatment is 0.45 mu m;
step two: adding the secondary biochemical tail water of the fermentation pharmaceutical wastewater after the microfiltration pretreatment into an ozone reactor, and then introducing O3-O2The ozone gas inflow amount of the mixed gas is 2Lmin-1The concentration of ozone in the intake air is 11.03mgL-1min-1And introducing a saturated potassium iodide KI solution at the tail end to remove residual ozone, wherein the reaction time is 30min, a reaction bin in the ozone reactor is made of machine glass, an ozone aeration porous plate is additionally arranged at the bottom end of the ozone reactor and is used for cutting ozone into small uniform bubbles and then contacting with wastewater to generate oxidation reaction, and an ultrasonic generator is added into the ozone reactor in the second step, and the ultrasonic frequency is 10 MHz.
Step three: and (2) washing the reverse osmosis system with reverse osmosis product water for 10min, adding a bactericide according to the ratio of 20mg/L, and introducing the effluent obtained in the step two into the reverse osmosis system, wherein the bactericide comprises the following components in parts by weight: 5 parts of fatty acid methyl ester, 4 parts of folium isatidis extract, 4 parts of radix isatidis extract, 3 parts of sodium chloride, 6 parts of coco betaine, 7 parts of citric acid-sodium citrate buffer solution, 8 parts of ethanol and 18 parts of distilled water, wherein the reverse osmosis duration is 30min, the molecular weight cut-off of a reverse osmosis membrane in a reverse osmosis system is 100Da, the operating pressure in the reverse osmosis system is 0.3MPa, after the reverse osmosis is finished, the reverse osmosis produced water is detected, and the detected reverse osmosis produced water is discharged after reaching the standard.
Example 7: the embodiment is carried out by taking secondary biochemical tail water of a pharmaceutical factory in antibiotic pharmaceutical industry as an object, and the method for deeply treating the secondary biochemical tail water of the fermented pharmaceutical wastewater comprises the following steps:
the method comprises the following steps: adding hydrochloric acid into the fermented pharmaceutical wastewater, adjusting pH of the fermented pharmaceutical wastewater to 3, adding iron-carbon particles with particle size of 3cm into the fermented pharmaceutical wastewater at a ratio of 50g/L3The mass ratio of iron to carbon is 28: 1, adding a catalyst into the fermented pharmaceutical wastewater according to the proportion of 20g/L, wherein the catalyst is 2mm3Activated carbon particles of (2), MnO2Mixing the powder and NaCl powder according to the mass ratio of 5:2:1, and pressing into 10mm3Electromagnetically stirring square particles for 50min, filtering after the electromagnetic stirring is finished, filtering by adopting a 120-mesh standard screen to obtain a filtrate, and adding a Fenton reagent into the obtained filtrate, wherein the Fenton reagent is FeCl2、H2O2、Na2C2O4Mixing according to the mass ratio of 1:2:1, performing secondary electromagnetic stirring, continuously stirring for 40min, irradiating by using ultraviolet rays with the wavelength of 70nm in the stirring process, wherein the irradiation intensity is 1500Lux, the adding amount of the Fenton reagent is 80mg per liter of water, and adding 4cm in the Fenton reagent treatment process3TiO2The particles are used as a catalyst of a photocatalytic oxidation method, and after secondary stirring is finished, microfiltration pretreatment is carried out on the secondary biochemical tail water of the fermented pharmaceutical wastewater by using a filter membrane, wherein the aperture of the filter membrane subjected to microfiltration pretreatment is 0.45 mu m;
step two: adding the secondary biochemical tail water of the fermentation pharmaceutical wastewater after the microfiltration pretreatment into an ozone reactor, and then introducing O3-O2The ozone gas inflow amount of the mixed gas is 2Lmin-1The concentration of ozone in the intake air is 11.03mgL-1min-1And introducing a saturated potassium iodide KI solution at the tail end to remove residual ozone, wherein the reaction time is 30min, a reaction bin in the ozone reactor is made of machine glass, an ozone aeration porous plate is additionally arranged at the bottom end of the ozone reactor and is used for cutting ozone into small uniform bubbles and then contacting with wastewater to generate oxidation reaction, and an ultrasonic generator is added into the ozone reactor in the second step, and the ultrasonic frequency is 10 MHz.
Step three: and (2) washing the reverse osmosis system with reverse osmosis product water for 10min, adding a bactericide according to the ratio of 20mg/L, and introducing the effluent obtained in the step two into the reverse osmosis system, wherein the bactericide comprises the following components in parts by weight: 5 parts of fatty acid methyl ester, 8 parts of folium isatidis extract, 9 parts of radix isatidis extract, 5 parts of sodium chloride, 7 parts of coco betaine, 8 parts of citric acid-sodium citrate buffer solution, 10 parts of ethanol and 20 parts of distilled water, wherein the reverse osmosis duration is 30min, the molecular weight cut-off of a reverse osmosis membrane in a reverse osmosis system is 100Da, the operating pressure in the reverse osmosis system is 0.5MPa, after the reverse osmosis is finished, the reverse osmosis produced water is detected, and the detected reverse osmosis produced water is discharged after reaching the standard.
And (4) analyzing results:
total organic carbon was determined by a total organic carbon analyzer (Shimadzu 5000-A).
The membrane flux refers to the volume of filtrate obtained by unit time unit membrane area, and can reflect the efficiency of the membrane module in treating wastewater. Can be calculated according to the formula:
wherein, J-Membrane flux, L m-2h-1(ii) a V is the sample volume, L; Δ T-temperature change, deg.C, before and after sampling; theta-sampling time, h; a-effective area of the film, m2。
Measurements were performed for each index and removal was calculated, with triplicate sets for all sample measurements and results expressed as mean ± standard deviation. C0Concentration of each index representing feed water before reaction, CtThe concentration of each index of the effluent is represented, and the removal rate is calculated as shown in the formula:
through analysis, the following results are obtained:
1. influence of ozone dosage on removal of soluble organic matters in secondary biochemical tail water of fermented pharmaceutical wastewater
The effect of ozone dosage on the removal of soluble organic substances in the secondary biochemical tail water of pharmaceutical wastewater is shown in FIG. 2, which shows the removal rate of soluble organic substances in the secondary biochemical tail water of fermented pharmaceutical wastewaterIncreasing with increasing ozone dosage. In view of the economical efficiency of the actual process operation, 11.03mgL is selected-1min-1The addition amount of the oxidant is the optimal addition amount.
2. Influence of operating pressure on flux of secondary biochemical tail water film of fermentation pharmaceutical wastewater treated by reverse osmosis membrane
The influence of the operating pressure on the flux of the secondary biochemical tail water film of the fermented pharmaceutical wastewater treated by the reverse osmosis membrane is shown in the figure, and the flux of the reverse osmosis membrane is increased along with the increase of the pressure, so that the operating pressure of the inlet water is selected to be 0.5MPa.
In conclusion, the method can effectively remove the soluble organic matters in the secondary biochemical tail water of the fermented pharmaceutical wastewater. It is thus shown that the various components and parameters of the process of the invention are the best choices and achieve the best results of the process of the invention.
Claims (9)
1. A method for advanced treatment of secondary biochemical tail water of fermented pharmaceutical wastewater is characterized by comprising the following steps:
the method comprises the following steps: adding hydrochloric acid into the fermented pharmaceutical wastewater, adjusting the pH of the fermented pharmaceutical wastewater to 3-3.5, and adding iron-carbon particles with a particle size of 2-3cm into the fermented pharmaceutical wastewater at a ratio of 50g/L3The mass ratio of iron to carbon is 15: 1-28: 1, adding a catalyst into the fermented pharmaceutical wastewater according to the proportion of 20g/L, performing electromagnetic stirring for 30-50min, filtering after the electromagnetic stirring is finished, filtering by adopting a standard sieve with the meshes of 100 and 120 to obtain a filtrate, and adding a Fenton reagent into the obtained filtrate, wherein the Fenton reagent is FeCl2、H2O2、Na2C2O4Mixing the raw materials according to a mass ratio of 1:2:1, performing secondary electromagnetic stirring, continuously stirring for 30-40min, irradiating by using ultraviolet rays with a wavelength of 10-150 nm during stirring, and performing microfiltration pretreatment on secondary biochemical tail water of the fermented pharmaceutical wastewater by using a filter membrane after secondary stirring is finished;
step two: adding the secondary biochemical tail water of the fermentation pharmaceutical wastewater after the microfiltration pretreatment into an ozone reactor, and then introducing O3-O2The ozone gas inflow amount of the mixed gas is 2Lmin-1The concentration of the ozone in the inlet air is 0-25.04mgL-1min-1Introducing saturated potassium iodide KI solution at the tail end to remove residual ozone, wherein the reaction time is 5-30 min;
step three: and (3) washing the reverse osmosis system with reverse osmosis product water for 8-10min, adding a bactericide according to the ratio of 20mg/L, introducing the effluent obtained in the step two into the reverse osmosis system, wherein the reverse osmosis time is 20-30min, detecting reverse osmosis produced water after the reverse osmosis is finished, and discharging the water after the reverse osmosis produced water reaches the standard.
2. The method for advanced treatment of secondary biochemical tail water of fermented pharmaceutical wastewater as claimed in claim 1, wherein the pore size of the filter membrane for microfiltration pretreatment of the secondary biochemical tail water of fermented pharmaceutical wastewater in the first step is 0.45 μm.
3. The method for advanced treatment of secondary biochemical tail water of fermented pharmaceutical wastewater as claimed in claim 1, wherein the catalyst in the first step is 1-2mm3Activated carbon particles of (2), MnO2Mixing the powder and NaCl powder according to the mass ratio of 5:2:1, and pressing into 8-10mm3Square particles.
4. The method for advanced treatment of secondary biochemical tail water of fermented pharmaceutical wastewater as claimed in claim 1, wherein the Fenton reagent is added in an amount of 50-80 mg/l water in the first step, and 3-5cm is added in the Fenton reagent treatment process3TiO2The particles act as a catalyst for the photocatalytic oxidation process.
5. The method for advanced treatment of secondary biochemical tail water of fermented pharmaceutical wastewater as claimed in claim 2, wherein an ultrasonic generator is added to the ozone reactor in the second step, and the ultrasonic frequency is 8-10 MHz.
6. The method for advanced treatment of secondary biochemical tail water of fermented pharmaceutical wastewater as claimed in claim 1, wherein the ultraviolet irradiation intensity in the first step is 1000-.
7. The method for advanced treatment of secondary biochemical tail water of fermented pharmaceutical wastewater according to claim 1, wherein the bactericide added in the third step is composed of the following components in parts by weight: 3-5 parts of fatty acid methyl ester, 3-8 parts of folium isatidis extract, 4-9 parts of radix isatidis extract, 2-5 parts of sodium chloride, 4-7 parts of coco betaine, 5-8 parts of citric acid-sodium citrate buffer solution, 3-10 parts of ethanol and 15-20 parts of distilled water.
8. The method for advanced treatment of secondary biochemical tail water of fermented pharmaceutical wastewater according to claim 1, wherein the operating pressure in the reverse osmosis system in the third step is in the range of 0-0.5 MPa.
9. The method for advanced treatment of secondary biochemical tail water of fermented pharmaceutical wastewater as claimed in claim 1, wherein 3-5cm is added during Fenton's reagent treatment3TiO2The particles act as a catalyst for the photocatalytic oxidation process.
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