CN113213714A - Raw material medicine wastewater treatment process - Google Patents
Raw material medicine wastewater treatment process Download PDFInfo
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- CN113213714A CN113213714A CN202110658268.4A CN202110658268A CN113213714A CN 113213714 A CN113213714 A CN 113213714A CN 202110658268 A CN202110658268 A CN 202110658268A CN 113213714 A CN113213714 A CN 113213714A
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Images
Classifications
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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
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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
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/043—Details
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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
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/048—Purification of waste water by evaporation
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- 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
- 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
- C02F2203/00—Apparatus and plants for the biological treatment of water, waste water or sewage
- C02F2203/006—Apparatus and plants for the biological treatment of water, waste water or sewage details of construction, e.g. specially adapted seals, modules, connections
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/02—Temperature
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
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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
- C02F2209/00—Controlling or monitoring parameters in water 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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/16—Total nitrogen (tkN-N)
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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
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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
- C02F2303/00—Specific treatment goals
- C02F2303/10—Energy recovery
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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
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
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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
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/30—Aerobic and anaerobic processes
- C02F3/302—Nitrification and denitrification 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
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
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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
- C02F3/00—Biological treatment of water, waste water, or sewage
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Abstract
The invention discloses a raw material medicine wastewater treatment process which is characterized by comprising a pretreatment stage and a biochemical treatment stage, wherein the pretreatment stage comprises an evaporation pretreatment stage and an advanced catalytic oxidation pretreatment stage. The invention has the beneficial effects that: the running cost of an enterprise is reduced while the stable running and the standard-reaching discharge of the system are ensured; the pretreatment part ensures that the rear-end treatment process has higher impact resistance; the problems of high salt, high COD and partial toxicity in the antibiotic raw material medicine wastewater are solved; ensuring the stable operation of a subsequent biochemical system; reducing the influence on the surrounding environment; the core process section, namely the low-temperature normal-pressure evaporation technology, adopts non-metallic materials, has stronger tolerance and wider application range, and reduces the investment cost; the technology has low evaporation temperature (60-80 ℃), does not need pretreatment, and reduces the operation cost; the technology adopts an external heat exchange system, and scaling and blockage are not easy to occur in the operation process.
Description
Technical Field
The invention relates to the field of environment-friendly water treatment, in particular to a process for treating raw material medicine wastewater.
Background
Currently, the definition of the drug substance api (active Pharmaceutical ingredient) in ICH Q7A is: any substance or mixture of substances intended for use in the manufacture of a medicament and, when used in pharmacy, becomes an active ingredient of the medicament. The raw material drugs are divided into two categories of chemical synthetic drugs and natural chemical drugs according to the sources of the raw material drugs. A large amount of wastewater can be generated in the production process of chemical raw material medicines, such as workshop process production wastewater, pipeline cleaning wastewater, wastewater generated by solid-liquid separation in a medicine extraction or refining process and the like, the wastewater is various and needs to be classified according to quality, the wastewater is complex in water quality, often contains dozens of or even hundreds of characteristic pollutants, is various in intermediate products, large in organic load, large in toxicity, high in salt content and large in water quality and water quantity fluctuation, and belongs to high-concentration organic wastewater difficult to biologically treat. For high organic high-salt wastewater, the COD content is usually about 200000/L or more, the TDS is about 100000ppm or more, especially for cephalo-type piperazinone acid wastewater, the COD can reach 360000 mg/L or more, the ammonia nitrogen is more than 20000/L, and a certain amount of sodium salt is also contained. The traditional treatment mode of the raw material medicine wastewater usually adopts a solvent extraction method, an adsorption method, a biological method, a membrane separation method, an incineration method, a double-effect evaporation, biochemistry, advanced oxidation and the like, but the methods all have the defects that the treatment cost cannot be reduced on the premise of ensuring the discharge reaching the standard, secondary pollution is not generated, and even the wastewater of individual categories cannot be treated.
Chinese patent document CN110526517A discloses a treatment process of pharmaceutical intermediate production wastewater, which comprises a pretreatment process, a biochemical treatment process and a deep treatment process, wherein the pretreatment process sequentially passes through a first low-temperature high-pressure distillation kettle, a second low-temperature high-pressure distillation kettle, a comprehensive wastewater collection tank, an evaporator, a condensate collection tank, an internal electrolytic tank, a fenton reaction tank and a combined precipitation and air flotation device for treatment. The biochemical treatment process comprises the steps of sequentially treating in a hydrolysis acidification tank, a UASB anaerobic reactor, an A/O biochemical treatment system and a secondary sedimentation tank. The advanced treatment process comprises the steps of sequentially treating the waste water by an ABFT aeration biological fluidization tank, a high-efficiency flocculation sedimentation tank, a rear-end Fenton reaction tank, a rear-end combined precipitation air floatation device, an intermediate water tank, a multi-medium filter, activated carbon filtration and a clean water tank, and finally discharging the waste water after reaching the standard.
However, the low-temperature high-pressure distillation kettle used in the process cannot meet the requirement of large water amount, the cost is high if the corrosion prevention requirement is met, the manufacturing period is long, and most importantly, the high-pressure condition has certain danger for medical intermediate wastewater.
The evaporator involved in the process has certain limits on the tolerance and tolerance range of the medical wastewater, and the treatment cost is high. A pre-treatment stageThe poor treatment effect of (2) can increase the load of the subsequent process, and cause the treatment to be not up to the standard. The Fenton reactor in the process can generate a large amount of sludge, the outsourcing cost is increased, and meanwhile, after COD reaches a certain removal rate, organic matters can not be removed any more, so that H is easily caused2O2Consumption of medication.
Therefore, a low-cost and stable-running raw material medicine wastewater treatment process is urgently needed in the prior art.
Disclosure of Invention
The invention aims to provide a process for treating raw material medicine wastewater, which aims to solve the problems in the prior art.
In order to achieve the purpose, the invention provides the following technical scheme:
a raw material medicine wastewater treatment process comprises a pretreatment stage and a biochemical treatment stage, wherein the pretreatment stage comprises an evaporation pretreatment stage and an advanced catalytic oxidation pretreatment stage.
Further, the evaporation pretreatment stage adopts a low-temperature normal-pressure evaporation process, and preferably, the low-temperature normal-pressure evaporation process adopts a non-metal material.
Further, an external heat exchange system is adopted in the evaporation pretreatment stage, and preferably, the external heat exchange system is provided with a heat energy recovery unit.
Further, the evaporation temperature of the evaporation pretreatment stage is 60-90 ℃; preferably, the evaporation temperature is preferably 80 to 90 ℃.
Further, the bulk drug is an antibiotic bulk drug.
Further, the advanced catalytic oxidation pretreatment stage is a graphene ozone catalytic oxidation process.
Further, the advanced catalytic oxidation pretreatment stage is used to treat high-concentration wastewater.
Further, the evaporation pre-treatment stage comprises the following steps:
the method comprises the steps of dividing raw material medicine wastewater into three types of high-salt high-organic wastewater, high-concentration wastewater and near-saturated high-salt wastewater, conveying the high-salt high-organic wastewater into low-pressure normal-temperature evaporation equipment by a water inlet pump, mixing the high-salt high-organic wastewater with circulating wastewater, then feeding the high-salt high-organic wastewater into a heat exchange system, heating the high-salt high-organic wastewater to an evaporation temperature, then feeding the high-salt high-organic wastewater into an evaporator to finish an evaporation process, and discharging evaporation gas from the top of the evaporator to enter a condenser to be condensed to form condensed effluent. The low-temperature normal-pressure system is used for processing to obtain evaporated water and a concentrated solution in a supersaturated state, the evaporated water enters a regulating tank, the concentrated solution is discharged into a concentrated solution storage tank with stirring, then the concentrated solution is transferred into an evaporation crystallizer through a lift pump for secondary evaporation, and miscellaneous salt and residues after secondary evaporation crystallization are subjected to outsourcing treatment; the nearly saturated high-salinity wastewater directly enters a crystallizer for evaporation, the evaporated water enters a regulating tank, and the crystallized miscellaneous salt and residues are treated outside.
Further, the advanced catalytic oxidation pretreatment stage comprises the steps of:
high enriched waste water is carried to senior catalytic oxidation unit by the pump and is handled, adds the catalyst, lets in ozone according to certain proportion, and the oxygen-containing functional group and the ozone reaction on graphite alkene surface, ozonolysis produce two kinds of active free radicals of superoxide radical and active oxygen, and the organic matter of quick oxidative degradation further decomposes the organic matter of difficult degradation into micromolecular substance, when getting rid of COD in the waste water, improves the biodegradability that can waste water. And the effluent treated by the advanced catalytic oxidation unit enters an adjusting tank.
Still further, the biochemical treatment stage comprises the steps of:
domestic wastewater, flushing water, initial rainwater and other low-concentration wastewater enter a regulating tank, are fully mixed with evaporated effluent and advanced catalytic oxidation effluent and then are conveyed to a UASB (upflow anaerobic sludge blanket) anaerobic reactor through a pump, the effluent of the anaerobic reactor enters an AOAO (argon oxygen) high-efficiency denitrification system, AOAO effluent enters a secondary sedimentation tank for mud-water separation, and the effluent is discharged after reaching the standard, wherein part of sludge in the secondary sedimentation tank flows back to the AOAO biochemical treatment system for circular treatment; preferably, the AOAO denitrification system comprises a bio-enzyme preparation and a bio-enzyme preparation carrier module.
Through last technical scheme, evaporation pretreatment stage has adopted low temperature ordinary pressure evaporation technology, utilizes water or light component organic matter to distribute the proportion difference under different temperatures in air and aquatic, draws out moisture or organic matter in follow waste water or solution, realizes that salt water separation or material purification retrieve, carries out under the ordinary pressure, and evaporating temperature is low.
The equipment in the evaporation pretreatment stage can be made of non-metallic materials, and has strong corrosion resistance, wide application range and low manufacturing cost; the equipment in the evaporation pretreatment stage adopts an external heat exchange system, unique optimized filler is selected in the external heat exchange system, a phase change interface and a heat transfer surface are separated, the structural performance is better, and scaling and blockage are not easy to occur; the tolerance to raw water is strong, the pretreatment requirement is low, direct liquid inlet of acid-base and electrochemical corrosion materials can be accepted, and the treatment cost is reduced; the external heat exchange system is also provided with a heat energy recovery unit, so that the energy consumption is low, and the treatment cost is further reduced. Meanwhile, the equipment in the evaporation pretreatment stage can be automatically controlled, is unattended and saves the labor cost.
In the technical scheme, the graphene-doped ozone catalytic oxidation process is adopted in the advanced catalytic oxidation pretreatment stage, so that the problem of COD (chemical oxygen demand) difficult to degrade is solved, and salinity can be controlled. Compared with ozone oxidation, the reaction rate of the hydroxyl free radical is high and is 10 times higher5The catalyst has no selectivity, can react with almost all organic matters, has stable catalytic effect and can not change along with the change of the residual organic matters in water. Graphene has catalytic ozone oxidation activity, can improve the effect of ozone oxidation degradation of organic pollutants, and has the following mechanism: oxygen-containing functional groups on the surface of the graphene can react with ozone, and the ozone is decomposed to generate two active free radicals, namely superoxide free radical and active oxygen, so that organic matters are quickly oxidized and degraded.
The graphene ozone catalytic oxidation process taking the graphene catalyst as the core has the following characteristics:
1) the catalytic efficiency is stable, and the service life of the catalyst is long. The metal particles of the catalyst are sintered on the surface of the porous inorganic material in the form of solid solution, the dissolution rate is low, the wear resistance is good, and the service life is more than 5 years;
2) the high-salt condition of the catalyst is improved through catalyst modification, and particularly, the oxidation efficiency of organic matters is kept under the conditions of high chlorine and high-salt particles;
3) the graphene-doped catalytic system greatly improves the ozone oxidation efficiency, enables the macromolecular organic matters which are difficult to degrade to be fully opened and broken, and achieves the effect of reducing COD in limited space time.
In conclusion, the graphene-doped ozone catalytic oxidation process has the advantages of high oxidation efficiency, low oxidation selectivity, high anti-interference capability and high targeted oxidation of organic matters.
In the above technical scheme, the AOAO high-efficiency denitrification process is adopted, and the biological strengthening treatment process of the AOAO high-efficiency denitrification process is suitable for upgrading and modifying of the traditional denitrification treatment process, such as the processes of AO, AAO, oxidation ditch and the like, or for upgrading and modifying of inverted AO, AAO, multi-point water inflow AAO, carrousel oxidation ditch and the like based on the change of the processes. In the technical scheme of the half aspect, the core module of the AOAO high-efficiency denitrification system comprises a biological enzyme preparation and a biological enzyme preparation carrier module. The AOAO high-efficiency denitrification system adopts a biological carrier, improves the aggregation behavior of microorganisms by utilizing the adsorption effect of the microorganisms, and leads the microorganisms with the capacity of degrading pollutants to be combined on the surface of the carrier according to certain structures and functions to form an aggregated microbial community, which can also be called as a biomembrane. The AOAO high-efficiency denitrification system adopts a biological carrier and a biological enzyme preparation carrier module as biological fillers, and has the advantages that: the specific surface area is large, the amount of microorganisms is large, the processing capacity is high, and the purification function is obviously improved; simultaneously, microorganisms are fixed, and the subsequent separation burden is reduced; has stronger biodegradability; impact load resistance, and strong adaptability to water quality and water quantity change; the operation and management are easy, the sludge expansion problem is reduced, and the sludge backflow and back washing of the filler are not needed; simple to operate, easily construction, and do not influence facility in the pond and overhaul.
The AOAO high-efficiency denitrification system adopts a biological enzyme preparation, and microorganisms firstly adsorb pollutants on the surfaces of cells of the microorganisms to enrich the pollutants by means of self organs; and various self-produced enzymes are utilized to decompose various pollutants. The removal of nitrogen is divided into three processes: under the anaerobic condition, organic nitrogen is converted into nitrogen through an ammoniation process under the action of anaerobic bacteriaAmmonia nitrogen; secondly, under aerobic conditions, ammonia nitrogen is firstly converted into nitrite nitrogen through nitrosation under the action of nitrite bacteria, and the nitrite nitrogen is converted into nitrate nitrogen through nitrification under the action of nitrate bacteria; and thirdly, under the anoxic condition, the nitrate nitrogen is converted into nitrogen or other gaseous nitrogen compounds through denitrification under the action of denitrifying bacteria. After the whole process is finished, the nitrogen element in the water body is changed into gaseous state from the dissolved state and is released into the air, and the purpose of reducing the content of the nitrogen element in the water body is achieved. In the whole conversion chain, whether nitrate nitrogen can be successfully converted into gaseous products such as nitrogen and the like through denitrification is one of the keys for removing the total nitrogen in the water body. The denitrification is performed by denitrifying bacteria. Most of the denitrifying bacteria are heterotrophic and facultative anaerobes, and the activity is strong under the conditions of low ambient oxygen concentration and high carbon source content. However, in the surface water environment, along with the gradual promotion of the treatment process, the dissolved oxygen content in the water body gradually rises, the content of the organic carbon source gradually decreases, the reaction environment at the moment is not suitable for heterotrophic facultative denitrifying bacteria, further removal of the total nitrogen content in the surface water is influenced, and the total nitrogen content is difficult to be reduced below the surface water standard. In order to solve the problems, the biological enzyme preparation adopted by the invention is particularly added with a class of autotrophic aerobic denitrifying bacteria. The denitrifying bacteria are denitrifying bacteria which utilize the action of aerobic denitrifying enzyme to carry out denitrification by assimilating carbon dioxide under aerobic condition. When the water environment is high dissolved oxygen and low organic matter environment, the nitrate nitrogen in the water body is oxidized into N by the special denitrifying bacteria in the process of assimilating carbon dioxide2O gas is released, and the effect of removing nitrogen elements in the water body is achieved. The denitrifying bacteria are added, so that an anoxic environment is not needed in the organic nitrogen removal process, the method is more suitable for further optimizing the surface water environment with relatively good water quality, and the nitrification and denitrification processes can be completed under an aerobic condition, so that the denitrification process is shortened, the total nitrogen removal efficiency is accelerated, and the standard reaching rate of wastewater treatment is ensured.
Compared with the prior art, the invention has the beneficial effects that:
1. by the technical scheme, the stable operation of the system is guaranteed, and the emission reaches the standard, and meanwhile, the operation cost of an enterprise is reduced;
2. the pretreatment part ensures that the rear-end treatment process has higher impact resistance;
3. the problems of high salt, high COD and partial toxicity in the antibiotic raw material medicine wastewater are solved;
4. ensuring the stable operation of a subsequent biochemical system;
5. reducing the influence on the surrounding environment;
6. the core process section, namely the low-temperature normal-pressure evaporation technology, adopts non-metallic materials, has stronger tolerance and wider application range, and reduces the investment cost; the technology has low evaporation temperature (60-80 ℃), does not need pretreatment, and reduces the operation cost; the technology adopts an external heat exchange system, and scaling and blockage are not easy to occur in the operation process.
Drawings
FIG. 1 is a flow chart of an exemplary embodiment of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1, according to an exemplary embodiment of the present invention, a process for treating wastewater containing pharmaceutical raw materials is provided, which includes a pretreatment stage and a biochemical treatment stage, wherein the pretreatment stage includes an evaporation pretreatment stage and an advanced catalytic oxidation pretreatment stage.
Preferably, the evaporation pretreatment stage adopts a low-temperature normal-pressure evaporation process, and preferably, the low-temperature normal-pressure evaporation process adopts a non-metallic material.
Preferably, an external heat exchange system is adopted in the evaporation pretreatment stage, and preferably, the external heat exchange system is provided with a heat energy recovery unit.
Preferably, the evaporation temperature of the evaporation pretreatment stage is 60-90 ℃; preferably, the evaporation temperature is preferably 80 to 90 ℃.
Preferably, the drug substance is an antibiotic drug substance.
Preferably, the advanced catalytic oxidation pretreatment stage is a graphene ozone catalytic oxidation process.
Preferably, the advanced catalytic oxidation pretreatment stage is used to treat high strength wastewater.
Preferably, the evaporation pre-treatment stage comprises the steps of:
the method comprises the steps of dividing raw material medicine wastewater into three types of high-salt high-organic wastewater, high-concentration wastewater and near-saturated high-salt wastewater, conveying the high-salt high-organic wastewater into low-pressure normal-temperature evaporation equipment by a water inlet pump, mixing the high-salt high-organic wastewater with circulating wastewater, then feeding the high-salt high-organic wastewater into a heat exchange system, heating the high-salt high-organic wastewater to an evaporation temperature, then feeding the high-salt high-organic wastewater into an evaporator to finish an evaporation process, and discharging evaporation gas from the top of the evaporator to enter a condenser to be condensed to form condensed effluent. The low-temperature normal-pressure system is used for processing to obtain evaporated water and a concentrated solution in a supersaturated state, the evaporated water enters a regulating tank, the concentrated solution is discharged into a concentrated solution storage tank with stirring, then the concentrated solution is transferred into an evaporation crystallizer through a lift pump for secondary evaporation, and miscellaneous salt and residues after secondary evaporation crystallization are subjected to outsourcing treatment; the nearly saturated high-salinity wastewater directly enters a crystallizer for evaporation, the evaporated water enters a regulating tank, and the crystallized miscellaneous salt and residues are treated outside.
Preferably, the advanced catalytic oxidation pretreatment stage comprises the steps of:
high enriched waste water is carried to senior catalytic oxidation unit by the pump and is handled, adds the catalyst, lets in ozone according to certain proportion, and the oxygen-containing functional group and the ozone reaction on graphite alkene surface, ozonolysis produce two kinds of active free radicals of superoxide radical and active oxygen, and the organic matter of quick oxidative degradation further decomposes the organic matter of difficult degradation into micromolecular substance, when getting rid of COD in the waste water, improves the biodegradability that can waste water. And the effluent treated by the advanced catalytic oxidation unit enters an adjusting tank.
Preferably, the biochemical treatment stage comprises the steps of:
domestic wastewater, flushing water, initial rainwater and other low-concentration wastewater enter a regulating tank, are fully mixed with evaporated effluent and advanced catalytic oxidation effluent and then are conveyed to a UASB (upflow anaerobic sludge blanket) anaerobic reactor through a pump, the effluent of the anaerobic reactor enters an AOAO (argon oxygen) high-efficiency denitrification system, AOAO effluent enters a secondary sedimentation tank for mud-water separation, and the effluent is discharged after reaching the standard, wherein part of sludge in the secondary sedimentation tank flows back to the AOAO biochemical treatment system for circular treatment; preferably, the AOAO denitrification system comprises a bio-enzyme preparation and a bio-enzyme preparation carrier module.
Example 1
The development, manufacture and sale of special medicines for mainly producing cephalosporin antibiotics and systems by a certain pharmaceutical company, various production wastewater is generated in the production process of raw material medicines, the products are different, the types and main pollutants of the generated wastewater are different, and the water quality of the wastewater of the raw material medicines of the antibiotics is shown in table 1 and is roughly divided into four types:
TABLE 1
The antibiotic raw material wastewater is treated according to the pretreatment stage and the biochemical treatment stage according to the treatment process shown in figure 1.
The antibiotic raw material medicine wastewater is classified into A, B, C, D types according to the water quality conditions, and classified collection is realized to realize quality-classified treatment.
Conveying the high-salt high-organic wastewater A to low-temperature normal-pressure evaporation equipment through a pump, feeding the evaporated water into a regulating tank, and conveying the evaporated concentrated solution to a final crystallizer through the pump; conveying the nearly saturated high-salt wastewater B to a final crystallizer through a pump to be evaporated and crystallized together with the concentrated solution of the wastewater A, introducing the effluent into an adjusting tank, separating the generated crystals through a centrifugal machine to obtain crystallized miscellaneous salt, and delivering residues to a unit with hazardous waste treatment quality for treatment, and introducing the mother liquor into the crystallizer for cyclic evaporation. The system treatment capacity of the low-temperature normal-pressure evaporation equipment is 100t/d, the water inflow is 5000kg/h, and the salt content of the inlet water is 12 percent. The concentration end point salt content of the low-temperature normal-pressure evaporation equipment is 40%, and the concentration multiple of the low-temperature normal-pressure evaporation equipment is 3.3 times. The evaporation temperature of the low-temperature normal-pressure evaporation equipment is 70-85 ℃, the use temperature of steam is 120-150 ℃, the use temperature of cooling water is 25-35 ℃, and the temperature of evaporated water is 35-40 ℃.
Conveying the wastewater C to a high-grade catalytic oxidation unit by a pump for treatment, adding a catalyst, and introducing ozone according to a certain proportion (the average 1g of ozone can remove 0.5-1.2 g of COD), wherein the specific surface area of the catalyst is 1.5 +/-0.2 square meters per gram, the strength is more than or equal to 650kgf/C square meters, the stacking porosity is more than or equal to 65%, and the stacking density is 1.5 +/-0.1 t/m3. Oxygen-containing functional groups on the surface of the graphene react with ozone, and the ozone decomposes to generate two active free radicals, namely superoxide radical and active oxygen, so that organic matters are quickly oxidized and degraded, the organic matters which are difficult to degrade are further decomposed into micromolecular substances, and COD in wastewater is removed, and the biodegradability of wastewater is improved. And the effluent treated by the advanced catalytic oxidation unit enters an adjusting tank.
Effluent quality of the pretreatment system is shown in table 2:
TABLE 2
After pretreatment, COD and TDS in the wastewater are obviously reduced, ammonia nitrogen and total nitrogen are reduced, and biodegradability is greatly improved.
Waste water D gets into low concentrated waste water collecting pit together with workshop tail gas tower waste water, recirculated cooling water, initial stage rainwater, domestic sewage, and after the balanced quality of water yield, discharge the equalizing basin together, go out the water mixing with the preliminary treatment, promote to UASB anaerobic reactor through the pump after the balanced quality of water yield, get rid of a large amount of organic pollutants in the waste water in UASB anaerobic reactor, go out water COD: 3200mg/L, TN: 450 mg/L.
The UASB system has 4 seats, and the size is: length, width, height, 8m, 7.5m, upward flow rate 0.5-0.6m/h, internal circulation maintained at 17.5 m/h3The checking load is 4.62kg/m3D. The effluent treated by the UASB anaerobic reactor enters an AOAO high-efficiency denitrification system which is formed by connecting two stages of anoxic tanks and aerobic tanks in series, and the single set of treated water volume is 500m3The aerobic tank is provided with a microporous aerator and an EPDM material, the MLSS is 3000mg/L, and the volume of the primary anoxic tank is 243m3The load is 1.5kgCOD/m3D, the volume of the first-stage aerobic tank is568m3The load is 1.5kgCOD/m3D, the volume of the secondary anoxic pond is 501m3The load is 1kgCOD/m3D, the volume of the secondary aerobic tank is 293m3The load is 1kgCOD/m3And d, decomposing pollutants in the wastewater by using microorganisms in an anoxic environment and an aerobic environment in sequence, reducing COD and simultaneously performing nitrogen and phosphorus removal. The total water retention time of the system is 4-7 days.
And (3) enabling the effluent treated by the AOAO high-efficiency denitrification system to enter a secondary sedimentation tank for sludge-water separation, settling and separating a biochemical sludge-water mixture, removing SS (suspended substances) to obtain clear effluent, refluxing a part of separated sludge to each section of biochemical tank through a sludge reflux pump, and discharging a part of residual aged sludge to a sludge concentration tank.
Biochemical section effluent quality table 3:
TABLE 3
After biochemical treatment, COD in the wastewater is further reduced, the removal rates of ammonia nitrogen, total nitrogen and total phosphorus are obvious, and the wastewater reaches the standard of garden nanotube.
Example 2
The method comprises the steps of treating the high-salt high-organic wastewater by a pharmaceutical company in Zhejiang, wherein the discharge amount of the high-salt high-organic wastewater is 30t/d, the discharge amount of the high-concentration wastewater is 50 t/d, and the discharge amount of the low-concentration wastewater is 120t/d, wherein the high-salt high-organic wastewater enters a low-temperature normal-pressure evaporator for evaporation concentration, a concentrated solution enters a crystallizer for crystallization, residues are subjected to external treatment, and evaporated water enters a regulating tank; high-concentration wastewater enters an advanced oxidation device, and effluent is discharged into a regulating tank; the low-concentration wastewater is collected and enters an adjusting tank to be mixed with evaporated effluent and advanced catalytic oxidation effluent, the mixture enters a biochemical system to be treated and then is discharged after reaching standards, and sludge is dewatered and then is subjected to external treatment.
Water intake index table 4:
| item | COD/(mg/L) | NH3-N/(mg/L) | Total nitrogen/(mg/L) | Total phosphorus/(mg/L) | TDS/ppm |
| High-salt and high-organic wastewater | 180000 | 7500 | 7500 | - | 120000 |
| High concentration waste water | 100000 | 200 | 250 | - | 20000 |
| Low concentration waste water | 600 | 20 | 25 | 30 | 200 |
TABLE 4
The effluent indexes after treatment are shown in table 5:
| item | COD/(mg/L) | NH3-N/(mg/L) | Total nitrogen/(mg/L) | Total phosphorus/(mg/L) | TDS/ppm |
| Index of water discharge | 450 | 33 | 35 | 1.2 | 1000 |
TABLE 5
In the embodiment, the removal rate of COD is 97%, the removal rate of ammonia nitrogen and total nitrogen is 95%, the removal rate of total phosphorus is more than 96%, and the removal rate of TDS is more than 99%. The raw material medicine wastewater treated by the system completely meets the discharge standard of the park nano-tube and can be directly discharged by the nano-tube.
In conclusion, in the technical scheme of the invention, the low-temperature normal-pressure evaporation concentration technology is combined with advanced catalytic oxidation, and in a system for treating the raw material wastewater by adopting the AOAO high-efficiency denitrification process, the removal efficiency of pollutants at each stage is high, the effect is obvious, and the quality of the wastewater discharged after treatment completely meets the garden nanotube standard and can be directly discharged by nanotubes.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The bulk drug wastewater treatment process is characterized by comprising a pretreatment stage and a biochemical treatment stage, wherein the pretreatment stage comprises an evaporation pretreatment stage and an advanced catalytic oxidation pretreatment stage.
2. The bulk drug wastewater treatment process of claim 1, wherein the evaporation pretreatment stage employs a low-temperature atmospheric evaporation process.
3. The bulk drug wastewater treatment process of claim 1, wherein an external heat exchange system is used in the evaporation pretreatment stage.
4. The bulk drug wastewater treatment process according to claim 1, wherein the evaporation temperature in the evaporation pretreatment stage is 60-90 ℃;
preferably, the evaporation temperature is preferably 80 to 90 ℃.
5. The bulk drug wastewater treatment process of claim 1, wherein the bulk drug is an antibiotic bulk drug.
6. The bulk drug wastewater treatment process of claim 1, wherein the advanced catalytic oxidation pretreatment stage is a graphene ozone catalytic oxidation process.
7. The bulk drug wastewater treatment process of claim 1, wherein the advanced catalytic oxidation pretreatment stage is used to treat high-concentration wastewater.
8. The bulk drug wastewater treatment process of any of claims 1-7, wherein the evaporation pretreatment stage comprises the steps of:
the method comprises the steps of dividing raw material medicine wastewater into three types of high-salt high-organic wastewater, high-concentration wastewater and near-saturated high-salt wastewater, conveying the high-salt high-organic wastewater into low-pressure normal-temperature evaporation equipment by a water inlet pump, mixing the high-salt high-organic wastewater with circulating wastewater, then feeding the high-salt high-organic wastewater into a heat exchange system, heating the high-salt high-organic wastewater to an evaporation temperature, then feeding the high-salt high-organic wastewater into an evaporator to finish an evaporation process, and discharging evaporation gas from the top of the evaporator to enter a condenser to be condensed to form condensed effluent. The low-temperature normal-pressure system is used for processing to obtain evaporated water and a concentrated solution in a supersaturated state, the evaporated water enters a regulating tank, the concentrated solution is discharged into a concentrated solution storage tank with stirring, then the concentrated solution is transferred into an evaporation crystallizer through a lift pump for secondary evaporation, and miscellaneous salt and residues after secondary evaporation crystallization are subjected to outsourcing treatment; the nearly saturated high-salinity wastewater directly enters a crystallizer for evaporation, the evaporated water enters a regulating tank, and the crystallized miscellaneous salt and residues are treated outside.
9. The bulk drug wastewater treatment process of claim 8, wherein the advanced catalytic oxidation pretreatment stage comprises the steps of:
high enriched waste water is carried to senior catalytic oxidation unit by the pump and is handled, adds the catalyst, lets in ozone according to certain proportion, and the oxygen-containing functional group and the ozone reaction on graphite alkene surface, ozonolysis produce two kinds of active free radicals of superoxide radical and active oxygen, and the organic matter of quick oxidative degradation further decomposes the organic matter of difficult degradation into micromolecular substance, when getting rid of COD in the waste water, improves the biodegradability that can waste water. And the effluent treated by the advanced catalytic oxidation unit enters an adjusting tank.
10. The bulk drug wastewater treatment process of claim 8, wherein the biochemical treatment stage comprises the steps of:
domestic wastewater, flushing water, initial rainwater and other low-concentration wastewater enter a regulating tank, are fully mixed with evaporated effluent and advanced catalytic oxidation effluent and then are conveyed to a UASB (upflow anaerobic sludge blanket) anaerobic reactor through a pump, effluent of the anaerobic reactor enters an AOAO (argon oxygen-oxygen) high-efficiency denitrification system, AOAO effluent enters a secondary sedimentation tank for mud-water separation, and effluent is discharged after reaching standards, wherein part of sludge in the secondary sedimentation tank flows back to the AOAO biochemical treatment system for circular treatment.
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