CN112851028A - Treatment method of chemical synthesis pharmaceutical wastewater - Google Patents
Treatment method of chemical synthesis pharmaceutical wastewater Download PDFInfo
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- CN112851028A CN112851028A CN202110060220.3A CN202110060220A CN112851028A CN 112851028 A CN112851028 A CN 112851028A CN 202110060220 A CN202110060220 A CN 202110060220A CN 112851028 A CN112851028 A CN 112851028A
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- wastewater
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- chemical synthesis
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Classifications
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
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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
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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
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
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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
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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Abstract
The invention discloses a method for treating chemical synthesis pharmaceutical wastewater, and belongs to the technical field of wastewater treatment and environmental protection. The treatment method is a combined process of a plurality of units, and mainly comprises the following steps: a catalytic oxidation unit, a biochemical property improving unit, a biodegradation unit, a biochemical property regeneration improving unit and a biological advanced treatment unit. The invention has reasonable process combination, low energy consumption, high efficiency and stable operation effect, and is suitable for treating the wastewater generated in the processes of completely chemically synthesizing pharmacy and semi-chemically synthesizing pharmacy.
Description
Technical Field
The invention relates to a method for treating pharmaceutical wastewater, in particular to a method for treating chemical synthesis pharmaceutical wastewater, and belongs to the technical field of environmental protection.
Background
The chemical synthetic pharmaceuticals refer to processes for producing pharmaceutical active ingredients using a chemical reaction or a series of chemical reactions, including fully synthetic pharmaceuticals and semi-synthetic pharmaceuticals. The production process generally comprises the steps of synthesizing chemical raw materials into a medical intermediate, then carrying out structural modification to form a target product, and then carrying out a series of steps of separation, refining, centrifugation, drying and the like to obtain a finished medicine product. The chemical synthetic drugs can be divided into inorganic synthetic drugs and organic synthetic drugs. The inorganic synthetic medicine is inorganic compound (very individual is element), such as aluminum hydroxide and magnesium trisilicate for treating gastric and duodenal ulcer; the organic synthetic medicine is mainly prepared from basic organic chemical raw materials through a series of organic chemical reactions (such as aspirin, chloramphenicol, caffeine, and the like). Many of the semi-synthetic antibiotics that have appeared in recent years are products of a combination of biological and chemical synthesis.
In the chemical synthesis pharmaceutical production process, sewage is generated in a plurality of links and has complex components, and the sewage mainly comprises process wastewater, such as crystallization mother liquor, phase inversion mother liquor, adsorption residual liquid and the like; and washing waste water such as washing water for reactors, filters, resin catalysts; and washing wastewater of the ground, tools and the like, wastewater of a vacuum system, backwash wastewater prepared from pure water and the like, and domestic sewage of workers and the like. The reason for serious pollution of chemical synthesis pharmacy is that the synthesis process is long, the reaction steps are many, the raw materials forming the chemical structure of the product only account for 5% -15% of the raw materials, the auxiliary raw materials and the like account for the vast majority of the raw materials, and finally most of the raw materials are converted into 'three wastes'. The pollutants of the chemical synthesis pharmaceutical wastewater are mainly conventional pollutants, namely pollutants such as COD, BOD, SS, pH, chromaticity and ammonia nitrogen, and residual products, reactants, catalysts, solvents, inorganic salts and the like in the chemical synthesis process, and have the characteristics of high pollutant concentration, poor biodegradability, biological toxicity and the like.
At present, a great deal of research is carried out on the treatment of pharmaceutical wastewater of chemical synthesis by various scholars at home and abroad, and the treatment method mainly comprises a physical-chemical method and a microbial degradation method. The physical and chemical method mainly comprises coagulating sedimentation, physical adsorption, advanced oxidation and the like, and mainly has the problems of high treatment cost, complex operation, easy secondary pollution, difficult standard-reaching effluent quality and the like. The microbial degradation method mainly comprises an anaerobic biological treatment method and an aerobic biological treatment method, wherein the anaerobic biological treatment method comprises processes of hydrolytic acidification, EGSB, UBF and the like, the aerobic biological treatment comprises processes of biological contact oxidation, CASS, SBR, A \ O and the like, and the microbial degradation method mainly has the defects of poor load resistance, easy absorption and inhibition of metabolic activity and inapplicability to the treatment of high-concentration organic wastewater. Therefore, the combination of the two, namely the physical and chemical pretreatment-anaerobic-aerobic biological treatment combined process, is mostly adopted at home and abroad. The combined process has the starting points of reducing the concentration of organic matters in the wastewater as much as possible through pretreatment and anaerobic treatment, simultaneously improving the biodegradability of the wastewater, cracking complex groups which are difficult to biodegrade, and enabling the subsequent aerobic biological treatment to stably operate.
Chinese patent application 201610549158.3 discloses a device and a method for treating chemical synthesis pharmaceutical wastewater, which employs a combination of complex enzymes and microorganisms to accelerate the biodegradation rate of organic substances in the wastewater, the complex enzymes used in the treatment method are complex in composition and complex in preparation process, and even if the high-concentration chemical synthesis pharmaceutical wastewater can be treated to reach the discharge standard, the acclimation and debugging time is up to four months, which is not suitable for large-scale industrial application.
Chinese patent application 201710259259.1 discloses a pretreatment method of antibiotics in antibiotic pharmaceutical wastewater and a treatment method of antibiotic pharmaceutical wastewater, wherein solid acid is added into the antibiotic pharmaceutical wastewater to carry out hydrolysis treatment on residual antibiotics, the method mainly explains the effect of removing the titer of a single antibiotic in laboratory simulation antibiotic wastewater, and the treatment of the complicated wastewater of a tetracycline pharmaceutical factory only explains the methane production amount of anaerobic microorganisms after hydrolysis treatment.
Chinese patent application 201811114940.8 discloses a treatment system and a treatment method for high-COD high-salt medical intermediate chemical wastewater, the method achieves its purpose through a series of steps such as air flotation, filtration, microelectrolysis, fenton, biochemistry and the like, because two stages of fiber filters are used for filtration, the treatment cost is increased, the problems of filter blockage, difficulty in replacement and the like are easily caused, and the treated wastewater has a high COD and still has a risk of harming the external environment.
Chinese patent application 201910896490.0 discloses a treatment process of pharmaceutical intermediate production wastewater, which comprises a pretreatment process, a biochemical treatment process and an advanced treatment process, wherein the process adopts a high-pressure distillation still concentration means at the front end to realize the purpose of wastewater pretreatment, and adopts a multi-media filter and activated carbon at the tail end to realize the purpose of wastewater standard discharge, so that the treatment cost of the pharmaceutical intermediate wastewater is greatly increased.
Chinese patent application 201911155361.2 discloses a method for treating high-concentration medical intermediate wastewater, and specifically relates to the steps of acidification, Fenton, anaerobic treatment, aerobic treatment and the like. Although the method realizes higher COD removal efficiency, the pH value needs to be adjusted to be very low and the temperature is increased due to the adoption of a two-stage or multi-stage acidification pretreatment process, so that the operation energy consumption is increased, the acid corrosion of wastewater treatment equipment is easily caused, and the equipment maintenance during the operation is not facilitated.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a method for treating pharmaceutical wastewater from chemical synthesis, namely a method for treating wastewater from complete chemical synthesis pharmacy and semi-chemical synthesis pharmacy, which can oxidize and degrade refractory organic matters in the wastewater and remove organic solvents and drug residues in the wastewater. The method is particularly suitable for treating the chemical synthesis pharmaceutical wastewater which has high organic matter concentration and poor biodegradability and is not suitable for being directly treated by a biological method, such as the treatment of chemical synthesis raw material medicines, chemical synthesis intermediates, semisynthetic raw material medicines combining chemical synthesis and biological synthesis and intermediate pharmaceutical wastewater, the treated effluent can reach GB 18918-2002 first-grade A standard, and can be directly discharged into rivers and lakes with smaller dilution capacity as urban landscape water.
Specifically, the technical scheme of the invention is realized as follows: a method for treating chemical synthesis pharmaceutical wastewater comprises the following steps:
(1) a catalytic oxidation unit:
discharging chemical synthesis pharmaceutical wastewater into an adjusting tank, adding dilute sulfuric acid or sodium hydroxide to adjust the pH value of the wastewater to 6.5-7.5, discharging the adjusted wastewater into a heterogeneous catalytic oxidation reaction tank, adding a catalyst and an oxidant into the wastewater, stirring for reaction for 5-8h, standing for 1-2h, and discharging supernatant into the next unit, wherein preferably, the catalyst is a composition of activated carbon, nitrate and sulfate, and the oxidant is one of ozone and ultraviolet light;
(2) a biochemical-improving unit:
discharging the wastewater treated in the step (1) into a multiphase Fenton oxidation tank, adding dilute sulfuric acid to adjust the pH value of the wastewater to 3.0-5.0, adding hydrogen peroxide and a catalyst into the wastewater to improve the biodegradability of the wastewater, stirring for 2-5h, standing for 1-2h, and discharging the supernatant into the next unit, wherein the catalyst is preferably a composition of white carbon black and metal oxide;
(3) a biodegradation unit:
discharging the wastewater treated in the step (2) into a hydrolysis acidification tank, adding sodium hydroxide to adjust the pH value of the wastewater to 6-8, stirring for reaction for 5-10h, discharging into a microbial electrochemical reaction tank, adding a carbon source, applying a voltage of 0.5-1.5v, stirring for 5-8h, allowing the mixture to enter a biological contact oxidation tank, controlling the dissolved oxygen to be 3-4mg/L, discharging the wastewater into a sedimentation tank for natural sedimentation after aeration reaction for 3-5h, discharging the supernatant into the next unit, preferably, the bioelectrochemical reaction tank is one of an up-flow anaerobic sludge bed-microbial electrolysis (UASB-MEC) reactor and an anaerobic baffle plate-microbial electrolysis (ABR-MEC) reactor, a carbon electrode is arranged in the bioelectrochemical reaction tank, the carbon electrode is one of a carbon fiber electrode, a carbon rod electrode, a carbon felt electrode and a carbon cloth electrode.
(4) A biochemical regeneration improving unit:
discharging the wastewater treated in the step (3) into an activation tank, adding a metal simple substance as an activating agent, adding persulfate, stirring and reacting for 3-8h, standing for 1-2h, and discharging the supernatant into the next unit, wherein preferably, the metal simple substance is one or a composition of simple substance iron, simple substance manganese and simple substance copper, and the persulfate is one or a composition of sodium persulfate and potassium persulfate.
(5) Biological advanced treatment unit:
and (3) discharging the wastewater treated in the step (4) into a biological aerated filter, adding dilute sulfuric acid or sodium hydroxide to adjust the pH value of the wastewater to 6-8, controlling the dissolved oxygen to be 3-4mg/L, and discharging the wastewater into a final sedimentation tank for natural sedimentation after an aeration reaction is carried out for 4-8 hours so as to reach the standard and discharge.
Furthermore, the adding amount of the activated carbon in the step (1) of the invention is 1-5mg/L, the adding amount of the nitrate and the sulfate is 0.5-2mg/L, the ratio of the nitrate to the sulfate is (1-3) to 1 (mass ratio), the nitrate is one or a combination of sodium nitrate, potassium nitrate and zinc nitrate, and the sulfate is one or a combination of sodium sulfate, potassium sulfate and zinc sulfate. Furthermore, the adding amount of the active carbon in the step (1) of the invention is 2-3mg/L, nitrate,The adding amount of the sulfate is 0.8-1.5mg/L, and the ratio of the nitrate to the sulfate is 2:1 (mass ratio); the oxidant is ultraviolet light with the wavelength range of 300-325nm and the irradiation dose of 80mJ/cm2. . Aiming at organic matters such as drug residues, organic solvents and the like in the wastewater, the organic matters are difficult to degrade and eliminate by using a conventional physical and chemical method and a conventional biological method, and the efficiency of a subsequent treatment unit is influenced. Therefore, under the catalytic action of activated carbon, nitrate and sulfate, the purpose of quickly and non-selectively removing the organic matters difficult to degrade in the wastewater can be realized by utilizing the OH with extremely strong oxidability generated in the water body by the ultraviolet light.
Further, the adding amount of hydrogen peroxide in the step (2) of the invention is 0.2-0.8mg/L, the adding amount of white carbon black is 1-5mg/L, the adding amount of metal oxide is 0.2-1.0mg/L, and the metal oxide is one of ferroferric oxide, copper oxide, zinc oxide and aluminum oxide or a composition thereof. Furthermore, the adding amount of the hydrogen peroxide in the step (2) is 0.4-0.6mg/L, the adding amount of the white carbon black is 2-4mg/L, and the adding amount of the metal oxide is 0.5-0.8 mg/L. Aiming at organic matters which are difficult to degrade in waste water, such as aromatic compounds, heterocyclic compounds and various synthetic intermediates, the organic matters which are difficult to biodegrade and have biotoxicity are easy to cause biotoxicity and biological inhibition effect on subsequent biological treatment. Therefore, on the basis of the traditional Fenton oxidation method, white carbon black is added as a catalytic carrier, and metal oxide is used for replacing Fe in the traditional Fenton reagent2+Therefore, the defects of the traditional Fenton oxidation method are improved, an efficient multiphase Fenton oxidation system is constructed, the residues of aromatic drugs, heterocyclic drugs and various synthetic intermediate drugs in the cracking wastewater can be efficiently and thoroughly realized, the biodegradability of the wastewater is greatly improved, and the stable operation of the subsequent biological treatment is facilitated.
Furthermore, the carbon source in step (3) of the present invention is one or a combination of glucose, sodium acetate and sodium lactate, the dosage is 3-10mg/L, and the applied voltage is 0.8-1.2 v. Furthermore, the adding amount of the carbon source in the step (3) of the invention is 5-8 mg/L. Aiming at complex chemical components in synthetic pharmaceutical wastewater, microorganisms in the traditional biological treatment process are difficult to metabolize and utilize, but the biological treatment process is still the main and the first choice of the water treatment process due to low price, high efficiency and broad spectrum applicability, so how to improve and optimize the traditional biological treatment process becomes a research hotspot in the field of water treatment at present. The method is characterized in that electrons generated by microbial degradation are transferred to an anode through a cell membrane and combined with an electron receptor on a cathode to generate reduction products such as hydrogen, methane and the like, upflow anaerobic sludge bed-microbial electrolysis (UASB-MEC) and anaerobic baffled plate-microbial electrolysis (ABR-MEC) are coupled systems combining the advantages of a biological treatment technology and an electrochemical oxidation/reduction technology, a proper carbon source is added into the systems, proper biological voltage and electrodes are applied, and the purposes of rapidly domesticating and culturing electrochemical active bacteria in wastewater, efficiently removing organic pollutants in the wastewater and having high economic benefit can be achieved.
Furthermore, the adding amount of the metal simple substance in the step (4) is 3-15mg/L, and the adding amount of the persulfate is 5-10 mg/L. Furthermore, the adding amount of the metal simple substance in the step (4) of the invention is 9-12mg/L, and the adding amount of the persulfate is 6-8 mg/L. Aiming at the synthetic pharmaceutical wastewater treated by the physicochemical-biological combined process, pollutants which can be degraded by microorganisms are basically eliminated, but the wastewater still has higher COD concentration and lower B \ C, and the direct discharge of the wastewater into an external environment still causes the pollution of water and soil, so the biodegradability of the wastewater needs to be further improved so as to be beneficial to the subsequent deep treatment by using a biological method. Sulfate radical (SO)4 -●) Has an oxidation-reduction potential equivalent to that of a hydroxyl radical (. OH), but SO4 -●Has wider pH application range, higher reaction selectivity and higher steady-state concentration, is not easy to be consumed by other water quality components, and is more beneficial to the degradation and elimination of organic pollutants. The persulfate (such as sodium persulfate and potassium persulfate) is activated by using metal simple substances (such as simple substance iron, simple substance manganese and simple substance copper), and the gradually released metal ions can slowly activate persulfate to generate SO4 -●Thereby realizing the purposes of degrading organic matters which are difficult to degrade in the wastewater and improving the biodegradability of the wastewater.
Further, the method for treating the chemical synthesis pharmaceutical wastewater comprises the following steps:
(1) a catalytic oxidation unit:
discharging the chemical synthesis pharmaceutical wastewater into an adjusting tank, adding dilute sulfuric acid or sodium hydroxide to adjust the pH value of the wastewater to 6.5-7.5, discharging the adjusted wastewater into a heterogeneous catalytic oxidation reaction tank, starting ultraviolet light with the wavelength range of 300-2Adding 2.6mg/L of activated carbon, 0.4mg/L of sodium nitrate, 0.3mg/L of potassium nitrate, 0.1mg/L of zinc nitrate, 0.15mg/L of sodium sulfate, 0.15mg/L of potassium sulfate and 0.1mg/L of zinc sulfate into the wastewater, stirring for reaction for 7 hours, standing for 1-2 hours, and discharging the supernatant into the next unit.
(2) A biochemical-improving unit:
discharging the wastewater treated in the step (1) into a multiphase Fenton oxidation tank, adding dilute sulfuric acid to adjust the pH value of the wastewater to 3.0-5.0, adding 0.55mg/L of hydrogen peroxide, 3.2mg/L of white carbon black, 0.1mg/L of ferroferric oxide, 0.15mg/L of copper oxide, 0.25mg/L of zinc oxide and 0.2mg/L of aluminum oxide into the wastewater, improving the biochemical property of the wastewater, stirring for reacting for 4h, and discharging the supernatant into the next unit after standing for 1-2 h.
(3) A biodegradation unit:
discharging the wastewater treated in the step (2) into a hydrolysis acidification tank, adding sodium hydroxide to adjust the pH value of the wastewater to 6-8, stirring and reacting for 5-10h, then discharging into an up-flow anaerobic sludge bed-microorganism electrolysis reactor, arranging a carbon fiber electrode inside, adding 3.5mg/L of glucose, 2.5mg/L of sodium acetate and 1mg/L of sodium lactate, applying a voltage of 1.0v, stirring and reacting for 6h, then discharging into a biological contact oxidation tank, controlling the dissolved oxygen to be 3-4mg/L, performing an aeration reaction for 4.5h, then discharging the wastewater into a sedimentation tank for natural sedimentation, and discharging the supernatant into the next unit.
(4) A biochemical regeneration improving unit:
discharging the wastewater treated in the step (3) into an activation tank, adding 5mg/L of elemental iron, 2mg/L of elemental manganese, 3mg/L of elemental copper, 4.2mg/L of sodium persulfate and 3mg/L of potassium persulfate, stirring for reacting for 6 hours, standing for 1-2 hours, discharging the supernatant into the next unit,
(5) biological advanced treatment unit:
and (3) discharging the wastewater treated in the step (4) into a biological aerated filter, adding dilute sulfuric acid or sodium hydroxide to adjust the pH value of the wastewater to 6-8, controlling the dissolved oxygen to be 3-4mg/L, carrying out an aeration reaction for 6.5 hours, discharging the wastewater into a final sedimentation tank, naturally settling, and discharging the wastewater which meets the standard.
According to the technical scheme for treating the chemical synthesis pharmaceutical wastewater, the reaction units are properly and reasonably combined, the cascade reaction is compact, the treatment efficiency is high, the process stability is good, the broad-spectrum applicability is strong, and the synergistic treatment effect of the chemical synthesis pharmaceutical wastewater is reflected. Therefore, the invention provides the application of the chemical synthesis pharmaceutical wastewater treatment method, namely the wastewater treatment method is suitable for the treatment of various complete chemical synthesis pharmaceutical and semi-chemical synthesis pharmaceutical wastewater.
Compared with the prior art, the technical scheme of the invention has unexpected technical effects, such as:
the invention relates to a method for treating chemical synthesis pharmaceutical wastewater, which mainly comprises the following steps: a catalytic oxidation unit, a biochemical property improving unit, a biodegradation unit, a biochemical property regeneration improving unit and a biological advanced treatment unit. The combination of all the treatment units is reasonable, the cascade reaction is skillfully connected, and tests show that the treatment method has the advantages of good stability, strong reproducibility, strong broad-spectrum applicability, obviously higher COD removal rate than the prior art and the like. The invention has reasonable process combination, low energy consumption, high efficiency and stable operation effect.
Compared with the prior art, the various catalysts and the compound combinations thereof, the activating agent and the compound combinations thereof related in the invention greatly improve the reaction efficiency and shorten the reaction time. The catalytic oxidation unit, the biochemical property improving unit and the biochemical property improving unit related by the invention are used for cracking organic matters which are difficult to degrade in the wastewater, such as cyclic compounds, heterocyclic compounds and polycyclic aromatic hydrocarbon substances, into small molecular substances to the maximum extent, so that the biotoxicity is reduced, and the biochemical property of the wastewater is improved, so that a series of biological treatment units which are matched with the catalytic oxidation unit, the biochemical property improving unit, the biological contact oxidation unit and the biological aerated filter are stably and efficiently operated, the operation cost is greatly reduced, and the stable standard discharge of the final effluent is realized. Compared with the means of improving the biochemical property of the wastewater by Fenton oxidation in the prior art, the method has the advantages of high biochemical property improving efficiency, short reaction time, small reagent dosage and the like. Compared with the prior art in which the iron-carbon micro-electrolysis, coagulating sedimentation or single advanced oxidation technology is used as a wastewater pretreatment means before biological treatment, the method has the advantages of strong broad-spectrum applicability, high-efficiency and thorough cracking of refractory organic matters, good synergistic treatment effect and the like.
The method for treating the chemically synthesized pharmaceutical wastewater has a good treatment effect on wastewater generated in the production process of completely chemically synthesized drugs such as sulfonamides, antipyretic analgesics and the like, semi-chemically synthesized drugs such as antibiotics, antitumor drugs, vitamins and the like and combinations thereof, and the treated wastewater meets the wastewater discharge standard. The method can be widely popularized and applied to the treatment of wastewater generated in the processes of full chemical synthesis pharmacy and semi-chemical synthesis pharmacy.
Drawings
FIG. 1 is a flow chart of the chemical synthesis pharmaceutical wastewater treatment process of the invention.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The present invention will be further illustrated by the following specific examples in conjunction with the flow chart of the chemical synthesis pharmaceutical wastewater treatment process of the present invention, and it should be understood by those skilled in the art that the present invention is not limited to these examples. The invention can simplify the treatment process, reduce the investment and reduce the operation cost by an overtaking mode for treating the organic wastewater with lower concentration and stable water quality; for pharmaceutical wastewater with high concentration and large water quality fluctuation, such as pharmaceutical wastewater of complete chemical synthesis system, semi-chemical synthesis pharmaceutical biopharmaceutical system and the like, the process has the advantages of enough flexibility and broad-spectrum adaptability for treatment, and stable standard discharge of external drainage.
To further validate the various catalysts and activators used in the present invention, a multi-conditional single-factor bench scale experiment was performed as follows:
(1) verification of catalyst use in heterogeneous catalytic oxidation reaction: the sulfonamide production wastewater and the pharmaceutical intermediate production wastewater treated by the single heterogeneous catalytic oxidation treatment step are verified, pharmaceutical wastewater of two pharmaceutical companies is adopted, and the wastewater indexes are that the sulfonamide production wastewater: COD is 9820 mg/L; wastewater from the production of pharmaceutical intermediates: COD is 11020 mg/L; mixing wastewater: the COD was 10416mg/L and the throughput was 500L each, and the combinations are shown in Table 1, using different combinations of catalysts, under otherwise identical test conditions and procedures.
TABLE 1 COD removal rate of wastewater treated by different catalyst combinations
The results of pilot experiments on the treatment of sulfonamide production wastewater and pharmaceutical intermediate production wastewater by a single heterogeneous catalytic oxidation treatment step show that: the COD removal rate of the combination of the activated carbon, the sodium nitrate, the potassium nitrate, the zinc nitrate, the sodium sulfate, the potassium sulfate and the zinc sulfate is over 62 percent, particularly the combination of the ratio of 52:8:6:2:3:3:2 is adopted, while the COD removal rate is reduced by adopting the combination of other ratios, and the COD removal rate is obviously reduced if the sulfate, the nitrate and the activated carbon are respectively removed from the catalyst combination. Especially, in the combination of removing the active carbon, the removal rate of COD is reduced to about 20 percent. Therefore, the catalyst in the combination of the catalysts in the heterogeneous catalytic oxidation reaction has a synergistic effect, and the organic matters which are difficult to degrade in the wastewater can be rapidly and non-selectively removed by utilizing the strong oxidizing property of OH.
(2) Validation of the use of the biochemical improvement catalyst: the sulfonamide wastewater and the medical intermediate wastewater after the heterogeneous catalytic oxidation treatment are treated in the single heterogeneous fenton oxidation treatment step, and the wastewater indexes are that the sulfonamide production wastewater: b \ C is 0.22; wastewater from the production of pharmaceutical intermediates: b \ C ═ 0.21, mixed wastewater: the throughput was 200L each with B \ C ═ 0.23, and the combinations are shown in table 2, using different combinations of catalysts, under otherwise identical test conditions and procedures.
TABLE 2B \ C increase rate of wastewater treatment with different catalyst combinations
The results of pilot experiments on sulfonamide wastewater and pharmaceutical intermediate wastewater after heterogeneous catalytic oxidation treatment in a single heterogeneous Fenton oxidation treatment step show that: the B \ C increasing rate of the combination of white carbon black, ferroferric oxide, copper oxide, zinc oxide and aluminum oxide is over 92 percent, particularly the ratio of 64:2:3:5:4 is adopted, the B \ C increasing rate is obviously reduced by adopting the combination of other ratios, if the white carbon black is removed from the catalyst combination, the B \ C increasing rate is rapidly reduced to below 40 percent, and only one or more of the ferroferric oxide, the copper oxide, the zinc oxide and the aluminum oxide are removed, so long as the ratio of the B \ C increasing rate to the white carbon black is proper, the B \ C increasing rate can still keep a higher level. Therefore, the combination of the catalysts in the biochemical improvement catalytic reaction constructs an efficient multiphase Fenton oxidation system, can efficiently crack organic matters which are difficult to degrade in the wastewater, and greatly improves the biodegradability of the wastewater.
(3) Verification of the use of the biochemical regeneration improving activator: verifying antibiotic and vitamin wastewater after biochemical treatment by single activated persulfate oxidation treatment, wherein the wastewater is respectively taken from A \ O effluent of a sewage treatment system of an antibiotic manufacturer and a sewage treatment system of a vitamin manufacturer, COD of the wastewater is 400-plus-500 mg/L, and the experiment only inspects the change of biochemical indexes (B \ C), wherein the antibiotic production wastewater: b \ C is 0.22; vitamin production wastewater: the amounts of B \ C ═ 0.21 and the treatment levels were 500L each, and the combinations are shown in table 3, using different combinations of activators, under otherwise identical test conditions and procedures.
TABLE 3B \ C enhancement of wastewater treatment with different combinations of activators
The results of pilot experiments on the treatment of biochemically treated antibiotic and vitamin wastewater by a single activated persulfate oxidation treatment step show that: the improvement rate of B \ C by adopting the combination of elemental iron, elemental manganese, elemental copper, sodium persulfate and potassium persulfate is over 86 percent, particularly the proportion of 25:10:15:21:15 is adopted, and the improvement rate of B \ C is obviously reduced by adopting the combination of other proportions, if persulfate and metal elemental substances are respectively removed from the catalyst combination, the improvement rate of B \ C is not improved, only one or more of elemental iron, elemental manganese and elemental copper are removed, or one of sodium persulfate and potassium persulfate is removed, and the improvement rate of B \ C can still keep a higher level as long as the total proportion of the metal elemental substance and the persulfate \ is proper. Therefore, under the condition of no persulfate (sodium persulfate and potassium persulfate) or no metal simple substance (simple substance iron, simple substance manganese and simple substance copper), the activation reaction can not occur, and sulfate radical (SO) can not be generated naturally4 -●) SO that the compound has no degradation performance on waste water, and the combination of the activating agent can effectively promote persulfate to generate sulfate radical (SO)4 -●) Thereby cracking refractory organics and improving the biodegradability of the wastewater.
(4) Unit combination rationality and cascade reaction linking verification:
the combined process of the invention is verified by removing part of the units and replacing part of the units to treat the antipyretic analgesic wastewater and the anti-tumor wastewater respectively. The waste water is respectively taken from pharmaceutical waste water of two pharmaceutical companies, and the indexes of the waste water are as follows: the COD is 8930 mg/L; anti-tumor production wastewater: the COD was 12110mg/L and the throughput was 1000L each, and the test was carried out under otherwise identical test conditions and procedures using different combinations of units, as shown in Table 4.
TABLE 4 verification of different unit combinations for treating wastewater
The results of the small-scale test of the unit combination and cascade reaction connection show that: the combined process is adopted to treat the antipyretic analgesic wastewater and the anti-tumor wastewater, the effluent is stable and reaches the standard (GB 18918-2002 first-grade A standard), and the total COD removal rate is up to 99.6 percent. After the biochemical property improving unit and the catalytic oxidation unit are respectively removed, due to the lack of the continuous treatment of heterogeneous catalytic oxidation and multiphase Fenton oxidation, the undegradable organic matters in the wastewater are accumulated, the biotoxicity is increased, the subsequent biochemical treatment efficiency is reduced, and the effluent cannot be discharged up to the standard; after the biochemical property improving unit is removed, the biochemical property of the wastewater is difficult to further improve due to lack of persulfate activation reaction, the subsequent biological treatment can not continuously degrade organic matters in the wastewater, and the effluent can not be discharged after reaching the standard; after the catalytic oxidation and the biochemical improvement are replaced by conventional iron-carbon micro-electrolysis or coagulating sedimentation, the COD (chemical oxygen demand) of the effluent is very high, the water quality chromaticity is high and turbid, and in the experimental process, the phenomena of activated sludge disintegration and sludge floating of a subsequent biological treatment system occur. It can be seen that the conventional iron-carbon micro-electrolysis or coagulating sedimentation method is difficult to crack the refractory organics in the wastewater, such as cyclic compounds, heterocyclic compounds and polycyclic aromatic hydrocarbon substances, into small molecular substances, thereby resulting in poor biodegradability of the wastewater, high biotoxicity and difficulty in ensuring the normal operation of subsequent biological treatment, and therefore, each processing unit in the combined process of the invention is absent and can not be simply replaced.
Example 1: a pharmaceutical factory in Jiangsu province is a medium-sized pharmaceutical enterprise mainly synthesizing chemical bulk drugs. The production wastewater contains benzene, toluene, chlorobenzene and other refractory organics, and the wastewater indexes are as follows: the COD concentration is 8000-13000mg/L, the BOD concentration is 2240-3640mg/L, NH3The concentration of-N is 550-872mg/L, the pH value is 6.2-6.8, the fluctuation range is small, the ratio of BOD to COD (B \ C) is less than 0.3, and the biodegradability is poor. The treatment method of the chemical synthesis pharmaceutical wastewater provided by the invention is adopted for treatment, and the specific treatment process is as follows:
a catalytic oxidation unit: discharging the pharmaceutical wastewater into an adjusting tank, adding sodium hydroxide to adjust the pH value of the wastewater to 6.5-7.5, discharging the adjusted wastewater into a heterogeneous catalytic oxidation reaction tank, starting ultraviolet light with the wavelength range of 300-325nm and the irradiation dose of 80mJ/cm2Adding 2.6mg/L of activated carbon, 0.4mg/L of sodium nitrate, 0.3mg/L of potassium nitrate, 0.1mg/L of zinc nitrate, 0.15mg/L of sodium sulfate, 0.15mg/L of potassium sulfate and 0.1mg/L of zinc sulfate into the wastewater, stirring for reaction for 7 hours, standing for 1-2 hours, and discharging the supernatant into the next unit. After the treatment of the treatment unit, a plurality of refractory organic matters in the wastewater are removed from the wastewater by OH with extremely strong oxidability and without selectivity, the COD removal rate is 62-65%, the BOD removal rate is 30-35%, and the B \ C removal rate is improved to more than 0.35.
A biochemical-improving unit: discharging the wastewater treated by the catalytic oxidation unit into a multiphase Fenton oxidation tank, adding sulfuric acid to adjust the pH value of the wastewater to 3.0-5.0, adding 0.55mg/L of hydrogen peroxide, 3.2mg/L of white carbon black, 0.1mg/L of ferroferric oxide, 0.15mg/L of copper oxide, 0.25mg/L of zinc oxide and 0.2mg/L of aluminum oxide into the wastewater, stirring for 4h, standing for 1-2h, and discharging the supernatant into the next unit. After the treatment of the treatment unit, the residues of aromatic compounds and various intermediate drugs in the wastewater are cracked, the biodegradability of the wastewater is greatly improved, the removal rate of COD is 20-30%, the removal rate of BOD is 22-27%, and B \ C is improved to more than 0.45.
A biodegradation unit: discharging the wastewater treated by the biochemical improvement unit into a hydrolysis acidification tank, adding sodium hydroxide to adjust the pH value of the wastewater to 6-8, stirring and reacting for 8 hours, then discharging into an upflow anaerobic sludge bed-microorganism electrolysis reactor, arranging a carbon fiber electrode inside, adding 3.5mg/L of glucose, 2.5mg/L of sodium acetate, 1mg/L of sodium lactate and 1.0v of external voltage, stirring and reacting for 6 hours, then feeding into a biological contact oxidation tank, controlling the dissolved oxygen to be 3-4mg/L, carrying out an aeration reaction for 4.5 hours, then discharging the wastewater into a sedimentation tank for natural sedimentation, and discharging the supernatant into the next unit. After the treatment of the treatment unit, most organic matters in the wastewater are metabolized and degraded by microorganisms, the COD removal rate is 92-96 percent, the BOD removal rate is 95-98 percent, but B \ C is reduced to 0.2, which shows that the amount of the organic matters which can be degraded by microorganisms in the effluent of the unit is very small.
A biochemical regeneration improving unit: discharging the wastewater treated by the biodegradation unit into an activation tank, adding 5mg/L of elemental iron, 2mg/L of elemental manganese, 3mg/L of elemental copper, 4.2mg/L of sodium persulfate and 3mg/L of potassium persulfate, stirring for reacting for 5 hours, standing for 1-2 hours, and discharging the supernatant into the next unit. After treatment in the treatment unit, in SO4 -●Under the action of the catalyst, the organic matters which are difficult to degrade in the wastewater are further cracked into small molecular organic matters, so that the biodegradability of the wastewater is improved. The COD removal rate is 33-37 percent, the BOD removal rate is 32-40 percent, and the B \ C is improved to be more than 0.4, which shows that the organic matters which are difficult to degrade in the unit effluent are cracked and converted into the organic matters with better biodegradability.
Biological advanced treatment unit: and (3) discharging the wastewater treated by the biochemical regeneration improving unit in the step (4) into an aeration biological filter, adding sulfuric acid or sodium hydroxide to adjust the pH value of the wastewater to 6-8, controlling the dissolved oxygen to be 3-4mg/L, and after 6.5 hours of aeration reaction, discharging the wastewater into a final sedimentation tank for natural sedimentation and discharging the wastewater after reaching the standard.
After the treatment of the treatment unit, most organic matters in the wastewater are metabolized and degraded by microorganisms, and the effluent quality is stable and good. COD removal rate is 85% -89%, BOD removal rate is 94% -98%, and the final effluent indexes are COD concentration 32-43mg/L, BOD concentration 4-7mg/L and NH3The concentration of N is 1-3mg/L, and the pH value is 6.7-7.2.
Example 2: a pharmaceutical factory in Shandong province is a medium-sized pharmaceutical enterprise mainly producing sulfonamides and antipyretic and analgesic drugs. The production wastewater contains refractory organic matters such as methanol, acetone, dichloromethane, aromatic hydrocarbon and the likeThe indexes of the waste water are as follows: COD concentration 9000-11000mg/L, BOD concentration 1890-2250mg/L, NH3The concentration of N is 420-505mg/L, the pH value is 6.5-7.2, the ratio of BOD to COD (B \ C) is less than 0.3, and the biodegradability is poor. The treatment method of the chemical synthesis pharmaceutical wastewater provided by the invention is adopted for treatment, and the specific treatment process is as follows:
a catalytic oxidation unit: discharging the pharmaceutical wastewater into an adjusting tank, discharging the uniformly mixed wastewater into a heterogeneous catalytic oxidation reaction tank, starting ultraviolet light with the wavelength range of 300-325nm and the irradiation dose of 80mJ/cm2Adding 1mg/L of activated carbon, 0.1mg/L of sodium nitrate, 0.1mg/L of potassium nitrate, 0.1mg/L of zinc nitrate, 0.1mg/L of sodium sulfate, 0.05mg/L of potassium sulfate and 0.05mg/L of zinc sulfate into the wastewater, stirring for reacting for 8 hours, and discharging the supernatant into the next unit after standing for 1-2 hours. After the treatment of the treatment unit, a plurality of refractory organic matters in the wastewater are removed from the wastewater by OH with strong oxidizability and non-selectivity, the COD removal rate is 60-63%, the BOD removal rate is 31-33%, and B \ C is increased to more than 0.33.
A biochemical-improving unit: discharging the wastewater treated by the catalytic oxidation unit into a multiphase Fenton oxidation tank, adding sulfuric acid to adjust the pH value of the wastewater to 3.0-5.0, adding 0.2mg/L of hydrogen peroxide, 1.0mg/L of white carbon black, 0.05mg/L of ferroferric oxide, 0.05mg/L of copper oxide, 0.05mg/L of zinc oxide and 0.05mg/L of aluminum oxide into the wastewater, stirring for 3h, standing for 1-2h, and discharging the supernatant into the next unit. After the treatment of the treatment unit, the residues of aromatic compounds and various intermediate drugs in the wastewater are cracked, the biodegradability of the wastewater is greatly improved, the removal rate of COD is 18-28%, the removal rate of BOD is 23-28%, and B \ C is improved to more than 0.43.
A biodegradation unit: discharging the wastewater treated by the biochemical improvement unit into a hydrolysis acidification tank, adding sodium hydroxide to adjust the pH value of the wastewater to 6-8, discharging into an anaerobic baffle plate-microbial electrolysis reactor after stirring and reacting for 9h, arranging a carbon felt electrode in the reactor, adding 2mg/L glucose, 1mg/L sodium lactate and 0.8v external voltage, feeding into a biological contact oxidation tank after stirring and reacting for 6h, controlling the dissolved oxygen to be 3-4mg/L, discharging the wastewater into a sedimentation tank after aeration reaction for 5h, and naturally settling, and discharging the supernatant into the next unit. After the treatment of the treatment unit, most organic matters in the wastewater are metabolized and degraded by microorganisms, the COD removal rate is 94-96%, the BOD removal rate is 92-96%, but B \ C is reduced to 0.22, which shows that little organic matters which can be degraded by microorganisms exist in the effluent of the unit.
A biochemical regeneration improving unit: discharging the wastewater treated by the biodegradation unit into an activation tank, adding 1mg/L of elemental iron, 1mg/L of elemental manganese, 1mg/L of elemental copper, 3mg/L of sodium persulfate and 2mg/L of potassium persulfate, stirring for 6 hours, standing for 1-2 hours, and discharging the supernatant into the next unit. After treatment in the treatment unit, in SO4 -●Under the action of the catalyst, the organic matters which are difficult to degrade in the wastewater are further cracked into small molecular organic matters, so that the biodegradability of the wastewater is improved. The COD removal rate is 36-40%, the BOD removal rate is 30-35%, and the B \ C removal rate is improved to be more than 0.4, which shows that organic matters which are difficult to degrade in the unit effluent are cracked and converted into organic matters with better biodegradability.
Biological advanced treatment unit: and (3) discharging the wastewater treated by the biochemical regeneration improving unit in the step (4) into an aeration biological filter, adding sulfuric acid or sodium hydroxide to adjust the pH value of the wastewater to 6-8, controlling the dissolved oxygen to be 3-4mg/L, and after 5 hours of aeration reaction, discharging the wastewater into a final sedimentation tank for natural sedimentation and discharging the wastewater after reaching the standard.
After the treatment of the treatment unit, most organic matters in the wastewater are metabolized and degraded by microorganisms, and the effluent quality is stable and good. The COD removal rate is 85-90 percent, the BOD removal rate is 94-97 percent, and the final effluent indexes are that the COD concentration is 33-45mg/L, the BOD concentration is 6-8mg/L and NH3The concentration of N is 2-4mg/L, and the pH value is 6.5-7.0.
Example 3: a pharmaceutical factory in Shandong province is a large pharmaceutical enterprise mainly used for producing antibiotics and synthesizing anti-tumor drugs. The production wastewater contains complex components such as methanol, acetone, dichloromethane, pyridine, aromatic hydrocarbon rings, heterocyclic rings and the like, contains substances such as nitro, nitrogen-based aromatic compounds and the like, has high toxicity, has an inhibiting effect on activated sludge, and has poor biodegradability. The indexes of the wastewater are as follows: COD concentration 9820-3The concentration of-N is 600-950mg/L, the pH value is 6.0-6.5, the water quality is acidic, the ratio of BOD to COD (B \ C) is about 0.2, and the biodegradability is poor. Adopt the bookThe invention relates to a method for treating chemical synthesis pharmaceutical wastewater, which comprises the following steps:
a catalytic oxidation unit: discharging the pharmaceutical wastewater into an adjusting tank, adding sodium hydroxide to adjust the pH value of the wastewater to 6.5-7.5, discharging the adjusted wastewater into a heterogeneous catalytic oxidation reaction tank, introducing ozone, introducing 60mg/L of air inlet concentration, 800mL/min of air inlet amount, introducing 2h of air inlet time, adding 5mg/L of activated carbon, 0.3mg/L of sodium nitrate, 0.4mg/L of potassium nitrate, 0.3mg/L of nitric acid, 0.4mg/L of sodium sulfate, 0.4mg/L of potassium sulfate and 0.2mg/L of zinc sulfate into the wastewater, stirring for reacting for 6h, and discharging the supernatant into the next unit after standing for 1-2 h. After the treatment of the treatment unit, a plurality of refractory organic matters in the wastewater are removed from the wastewater by OH with extremely strong oxidability and without selectivity, the COD removal rate is 66-68%, the BOD removal rate is 30-35%, and the B \ C removal rate is improved to more than 0.3.
A biochemical-improving unit: discharging the wastewater treated by the catalytic oxidation unit into a multiphase Fenton oxidation tank, adding sulfuric acid to adjust the pH value of the wastewater to 3.0-5.0, adding 0.8mg/L of hydrogen peroxide, 5mg/L of white carbon black, 0.3mg/L of ferroferric oxide, 0.3mg/L of copper oxide, 0.2mg/L of zinc oxide and 0.2mg/L of aluminum oxide into the wastewater, stirring for 4h, standing for 1-2h, and discharging the supernatant into the next unit. After the treatment of the treatment unit, the residues of aromatic compounds and various intermediate drugs in the wastewater are cracked, the biodegradability of the wastewater is greatly improved, the removal rate of COD is 25-32%, the removal rate of BOD is 24-28%, and B \ C is improved to more than 0.35.
A biodegradation unit: discharging the wastewater treated by the biochemical improvement unit into a hydrolysis acidification tank, adding sodium hydroxide to adjust the pH value of the wastewater to 6-8, discharging the wastewater into an upflow anaerobic sludge bed-microbial electrolysis reactor after stirring and reacting for 8 hours, arranging a carbon fiber electrode in the reactor, adding 5mg/L of glucose and 5mg/L of sodium acetate, applying an external voltage of 1.2v, stirring and reacting for 7 hours, then feeding the wastewater into a biological contact oxidation tank, controlling the dissolved oxygen to be 3-4mg/L, discharging the wastewater into a sedimentation tank after an aeration reaction for 6 hours for natural sedimentation, and discharging the supernatant into the next unit. After the treatment of the treatment unit, most organic matters in the wastewater are metabolized and degraded by microorganisms, the COD removal rate is 95-98%, the BOD removal rate is 95-97%, but B \ C is reduced to 0.26, which shows that little organic matters which can be degraded by microorganisms exist in the effluent of the unit.
A biochemical regeneration improving unit: discharging the wastewater treated by the biodegradation unit into an activation tank, adding 10mg/L of elemental iron, 2mg/L of elemental manganese, 3mg/L of elemental copper, 6mg/L of sodium persulfate and 4mg/L of potassium persulfate, stirring for reacting for 6 hours, standing for 1-2 hours, and discharging the supernatant into the next unit. After treatment in the treatment unit, in SO4 -●Under the action of the catalyst, the organic matters which are difficult to degrade in the wastewater are further cracked into small molecular organic matters, so that the biodegradability of the wastewater is improved. The COD removal rate is 40-43 percent, the BOD removal rate is 42-45 percent, and the B \ C is improved to be more than 0.35, which shows that the organic matters which are difficult to degrade in the unit effluent are cracked and converted into the organic matters with better biodegradability.
Biological advanced treatment unit: and (3) discharging the wastewater treated by the biochemical regeneration improving unit in the step (4) into an aeration biological filter, adding dilute sulfuric acid or sodium hydroxide to adjust the pH value of the wastewater to 6-8, controlling the dissolved oxygen to be 3-4mg/L, and discharging the wastewater into a final sedimentation tank after 8 hours of aeration reaction for natural sedimentation to reach the standard and discharging.
After the treatment of the treatment unit, most organic matters in the wastewater are metabolized and degraded by microorganisms, and the effluent quality is stable and good. The COD removal rate is 88-92 percent, the BOD removal rate is 96-99 percent, and the final effluent indexes are that the COD concentration is 35-42mg/L, the BOD concentration is 3-7mg/L and NH3The concentration of N is 1-3mg/L, and the pH value is 7.0-7.4.
Claims (10)
1. The method for treating the chemical synthesis pharmaceutical wastewater is characterized by mainly comprising the following steps of:
(1) a catalytic oxidation unit:
discharging the chemically synthesized pharmaceutical wastewater into an adjusting tank, adding dilute sulfuric acid or sodium hydroxide to adjust the pH value of the wastewater to 6.5-7.5, discharging the adjusted wastewater into a heterogeneous catalytic oxidation reaction tank, adding a catalyst and an oxidant into the wastewater, stirring for reaction for 5-8h, standing for 1-2h, and discharging the supernatant into the next unit;
(2) a biochemical-improving unit:
discharging the wastewater treated in the step (1) into a multiphase Fenton oxidation tank, adding dilute sulfuric acid to adjust the pH value of the wastewater to 3.0-5.0, adding hydrogen peroxide and a catalyst into the wastewater to improve the biodegradability of the wastewater, stirring for 2-5h, and discharging supernatant into the next unit after standing for 1-2 h;
(3) a biodegradation unit:
discharging the wastewater treated in the step (2) into a hydrolysis acidification tank, adding sodium hydroxide to adjust the pH value of the wastewater to 6-8, stirring for 5-10h, then discharging into a microbial electrochemical reaction tank, adding a carbon source, applying a voltage of 0.5-1.5v, stirring for 5-8h, then discharging into a biological contact oxidation tank, controlling the dissolved oxygen to be 3-4mg/L, performing aeration reaction for 3-5h, then discharging the wastewater into a sedimentation tank for natural sedimentation, and discharging the supernatant into the next unit;
(4) a biochemical regeneration improving unit:
discharging the wastewater treated in the step (3) into an activation tank, adding a metal simple substance as an activating agent, adding persulfate, stirring for reacting for 3-8h, standing for 1-2h, and discharging the supernatant into the next unit;
(5) biological advanced treatment unit:
and (3) discharging the wastewater treated in the step (4) into a biological aerated filter, adding dilute sulfuric acid or sodium hydroxide to adjust the pH value of the wastewater to 6-8, controlling the dissolved oxygen to be 3-4mg/L, and discharging the wastewater into a final sedimentation tank for natural sedimentation after an aeration reaction is carried out for 4-8 hours so as to reach the standard and discharge.
2. The method for treating chemically synthesized pharmaceutical wastewater according to claim 1, wherein the catalyst in step (1) is a combination of activated carbon, nitrate and sulfate, preferably the nitrate is one or a combination of sodium nitrate, potassium nitrate and zinc nitrate, preferably the sulfate is one or a combination of sodium sulfate, potassium sulfate and zinc sulfate; the oxidant is one of ozone and ultraviolet light.
3. The method for treating wastewater from chemical synthesis of pharmaceuticals according to claim 2, wherein the amount of activated carbon added in step (1) is 1-5mg/L, and the amount of nitrate and sulfate added is 0.5-2 mg/L; preferably, the adding amount of the activated carbon is 2-3mg/L, and the adding amount of the nitrate and the sulfate is 0.8-1.5 mg/L.
4. The method for treating wastewater from chemical synthesis-based pharmaceutical production according to claim 3, wherein the ratio of nitrate to sulfate is 2:1 (mass ratio); preferably, the ratio of the nitrate to the sulfate is (1-3):1 (mass ratio).
5. The method for treating pharmaceutical wastewater generated in chemical synthesis according to claim 1, wherein the catalyst in step (2) is a combination of white carbon black and metal oxide, preferably the metal oxide is one of ferroferric oxide, copper oxide, zinc oxide and aluminum oxide or a combination thereof; preferably, the adding amount of the white carbon black is 1-5mg/L, and the adding amount of the metal oxide is 0.2-1.0 mg/L.
6. The method for treating pharmaceutical wastewater in chemical synthesis according to claim 1, wherein the amount of hydrogen peroxide added in step (2) is 0.2-0.8mg/L, preferably 0.4-0.6mg/L, 2-4mg/L and 0.5-0.8 mg/L.
7. The method for treating chemically synthesized pharmaceutical wastewater according to claim 1, wherein the bioelectrochemical reaction tank of the step (3) is one of an upflow anaerobic sludge blanket-microbial electrolysis (UASB-MEC) reactor and an anaerobic baffled plate-microbial electrolysis (ABR-MEC) reactor, and a carbon electrode is arranged inside the bioelectrochemical reaction tank; preferably, the carbon electrode is one of a carbon fiber electrode, a carbon rod electrode, a carbon felt electrode and a carbon cloth electrode.
8. The method for treating wastewater from chemical synthesis of pharmaceuticals according to claim 1, wherein the carbon source in step (3) is one or a combination of glucose, sodium acetate and sodium lactate, the dosage is 3-10mg/L, and the applied voltage is 0.8-1.2 v; preferably, the dosage of the carbon source is 5-8 mg/L.
9. The method for treating wastewater from chemical synthesis pharmacy according to claim 1, wherein in step (4), the elemental metal is one of elemental iron, elemental manganese and elemental copper or a combination thereof, and the persulfate is one of sodium persulfate and potassium persulfate or a combination thereof.
10. The method for treating pharmaceutical wastewater in chemical synthesis according to claim 1, wherein the amount of the metal simple substance added in the step (4) is 3-15mg/L, and the amount of the persulfate added is 5-10 mg/L; preferably, the adding amount of the metal simple substance is 9-12mg/L, and the adding amount of the persulfate is 6-8 mg/L.
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