CN107777830B - High-concentration degradation-resistant pharmaceutical wastewater treatment method and system - Google Patents

High-concentration degradation-resistant pharmaceutical wastewater treatment method and system Download PDF

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CN107777830B
CN107777830B CN201610756507.9A CN201610756507A CN107777830B CN 107777830 B CN107777830 B CN 107777830B CN 201610756507 A CN201610756507 A CN 201610756507A CN 107777830 B CN107777830 B CN 107777830B
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reactor
wastewater
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宣颖
邹洪波
邹亚波
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Beijing Anyutong Environment Engineering & Technology Co ltd
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    • C02F1/00—Treatment of water, waste water, or sewage
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    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
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    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
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    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
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    • 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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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/02—Aerobic processes
    • C02F3/12—Activated sludge processes
    • C02F3/1205—Particular type of activated sludge processes
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    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/28—Anaerobic digestion processes
    • C02F3/284—Anaerobic digestion processes using anaerobic baffled reactors
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/28—Anaerobic digestion processes
    • C02F3/2846—Anaerobic digestion processes using upflow anaerobic sludge blanket [UASB] reactors
    • 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
    • C02F3/28—Anaerobic digestion processes
    • C02F3/286—Anaerobic digestion processes including two or more steps

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Abstract

The application discloses a method and a system for treating high-concentration refractory pharmaceutical wastewater, wherein the treatment method comprises a pretreatment section and a biological reaction stage, the pretreatment section adopts a double-electric process of an electrolytic cell and a micro-electrolysis reaction tower to partially decompose and partially directly degrade refractory pollutants, remove toxic substances and lay a foundation for biological reaction; the biological section adopts hydrolytic acidification, an anaerobic reactor, high-load aerobic biochemical treatment and P-MBR deep aerobic biochemical treatment, and the P-MBR can prolong the retention time of pollutants, remove stubborn COD and reduce the influence of toxic and harmful substances, and has the advantages of strong impact resistance, high flexibility and good decolorizing and deodorizing effects.

Description

High-concentration degradation-resistant pharmaceutical wastewater treatment method and system
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a method and a system for treating high-concentration refractory pharmaceutical wastewater.
Background
The prior pharmaceutical wastewater is pretreated by adopting an advanced oxidation process to reduce the content of organic matters, then enters into biochemical treatment, is subjected to anaerobic reaction to degrade COD, then enters into an aerobic biological tank to further degrade the COD, and is discharged.
The pharmaceutical wastewater components are more and more complex, the pollutant structure is more and more stable, the water outlet requirement is continuously improved, the dosage of the conventional pretreatment process is large, the sludge amount is large, the operation cost is greatly improved, and the subsequent conventional biological treatment process cannot meet the water outlet requirement.
At present, the common pretreatment technology is an advanced oxidation technology, mature and applied Fenton reagent, ozone oxidation and the like, and biological treatment technology such as CASS technology and a biological activated carbon method. However, these processes have limitations.
When the Fenton reaction is used as a pretreatment process of high-concentration degradation-resistant wastewater, the amount of the added medicament is large, so that the operation cost is high; in addition, due to the particularity of the hydrogen peroxide, the storage and transportation requirements are strict, and the operation difficulty is large. The ozone oxidation adopts gas-liquid two-phase countercurrent operation to strengthen the mass transfer process, has lower efficiency and has high requirements on a generator and a reactor. The CASS process which is widely applied to the biological treatment process in the pharmaceutical wastewater integrates reaction, precipitation and water drainage, so that the degradation of pollutants is a flow pushing process in time, the volume utilization rate is low, the equipment idle rate is high, the control mode is single, and the requirement on the reliability of an automatic control system is high. When the biological activated carbon method is adopted, a large amount of activated carbon in the system is easily carried out of the system when yielding water, and even if a large amount of flocculating agent is added, part of the activated carbon still runs off, so that the operation cost is increased.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method and a system for treating high-concentration refractory pharmaceutical wastewater, aiming at treating the pharmaceutical wastewater which has high pollutant concentration, poor biodegradability and difficult biodegradation.
In order to solve the technical problem, the invention provides a method for treating high-concentration refractory pharmaceutical wastewater, which comprises the following steps:
step 1), high-concentration degradation-resistant pharmaceutical wastewater enters an adjusting tank to be mixed and adjusted in water quantity and water quality: the retention time in the regulating tank is 12-24 hours, the pH is regulated to be 4-7, and the mixture enters an electrolytic tank after being regulated;
step 2) carrying out electrolysis in an electrolytic cell: the electrolytic cell adopts a Ti-based PbO 2 coating electrode as an anode, a stainless steel electrode is used as a cathode, heavy metals in the wastewater are electrodeposited, the electrolysis time is 4 hours, the voltage is 4V, the current is 4-6A, the COD removal rate is 30-45%, cyanides and heavy metals such as copper, lead and zinc are removed, and the wastewater enters a micro-electrolysis reaction tower after being electrolyzed;
step 3) carrying out micro-electrolysis reaction in a micro-electrolysis reaction tower; the method comprises the following steps that the waste water stays in a micro-electrolysis reaction tower for 3-5 hours, iron-carbon efficient filler is filled in the micro-electrolysis reaction tower, the filler is sintered at 1300 ℃, and the filler comprises the following chemical components: refined iron powder not less than 75%, carbon content 17%, catalyst 5%, activator 3%, specific gravity 1.0t/m3Specific surface area 1.2m2G, porosity of 65%, physical strength ≧ 1000kg/cm2；
Step 4) adding a coagulant and a flocculant into the adjusting tank: adjusting the pH of effluent after micro-electrolysis reaction to 6-8, adding 30-50 mg/l of coagulant PFS and 5mg/l of flocculant PAM into the wastewater, reacting with suspended matters in the wastewater for 15-20 min, entering an inclined tube efficient sedimentation tank for mud-water separation, and pressurizing supernatant to a hydrolysis acidification unit by a pump;
step 5) processing in a hydrolysis acidification unit: hydrolysis acidification unit is anaerobic environment, dwell time 10h, adopt combined type baffling board reactor type among this hydrolysis acidification unit, the built-in vertical guide plate of reactor, separate into the reactor a plurality of reaction chambers of establishing ties, every reaction chamber all is a relatively independent upflow mud bed system, waste water rivers are advanced by baffle guide upper and lower baffling, pass through the mud bed in the reaction chamber one by one, the substrate in the aquatic fully contacts with the microorganism, the quantity of reaction chamber is 6 ~ 8, the aspect ratio of the upflow room along rivers advancing direction of reactor is at 1: 1-1: 2, the aspect ratio is 1: 3, erecting a semi-soft plastic fiber filler in the upper space of the reaction chamber, arranging a sludge discharge perforated pipe in the middle of the reactor, arranging a slag discharge pipe at the bottom of the reactor, and feeding the effluent of the hydrolysis acidification unit into an anaerobic reactor;
step 6) carrying out anaerobic reaction in an anaerobic reactor: the anaerobic reactor adopts a carbon steel anti-corrosion tower structure, and the volume load is 4-10 kgCOD/m3D, ascending flow rate: 0.9-1.1m/h, head loss: 0.76m, the pH value of the sewage entering the anaerobic reactor is between 6.5 and 8, the tower body is heated and insulated to control the water temperature to be 30 ℃, polyurethane filler is adopted, water is distributed by a perforated pipe, the diameter of a water distribution hole is phi 15mm, and the service area of each hole is 1 to 2m2The water is discharged from the open channel, and the water discharged from the anaerobic reactor enters a high-load aerobic tank;
step 7) carrying out aerobic reaction in a high-load aerobic tank: the combined filler is suspended in the high-load aerobic tank, the surface of the filler is full of a biological membrane, the filling rate is 70 percent, and the volume load of the filler is 0.5-3.0 kgBOD/m3D, filling the pool with dissolved oxygen of 3-6 mg/L, supplying air into water through an air blower and a microporous disc aerator, wherein the air-water ratio is 40-100: 1, carrying out aerobic reaction in a high-load aerobic pool, and then carrying out mud-water treatment in an inclined plate sedimentation poolSeparating and then entering a P-MBR deep aerobic biochemical section;
step 8) carrying out deep aerobic reaction in the P-MBR deep aerobic biochemical section: in the P-MBR deep aerobic biochemical section, refractory organic matters in the wastewater are removed through biological metabolism of activated sludge and adsorption of active fillers, wherein the microbial biomass is more than 10g/L, and the gas-water ratio is as follows: 20:1, membrane flux: 13-15L/m2H, the particle size of the active filler is 100um, the pore diameter of the membrane is 0.04um, and the treated wastewater can be discharged.
The invention also discloses a high-concentration degradation-resistant pharmaceutical wastewater treatment system, which comprises an adjusting tank, an electrolytic tank, a micro-electrolysis reaction tower, an adjusting tank, a hydrolysis acidification unit, an anaerobic reactor, a high-load aerobic tank and a P-MBR deep aerobic biochemical section which are connected in sequence, wherein,
the adjusting tank is used for mixing and adjusting the water quantity and the water quality of the wastewater, the pH value in the adjusting tank is 4-7, and a water outlet of the adjusting tank is connected with a water inlet of the electrolytic tank;
the electrolytic cell adopts a Ti-based PbO 2 coating electrode as an anode, a stainless steel electrode as a cathode, heavy metals in the wastewater are electrodeposited, the electrolysis time is 4h, the voltage is 4V, the current is 4-6A, and a water outlet of the electrolytic cell is connected with a water inlet of the micro-electrolysis reaction tower;
the micro-electrolysis reaction tower is filled with iron-carbon efficient filler, the filler is sintered at 1300 ℃, and the filler comprises the following chemical components: refined iron powder not less than 75%, carbon content 17%, catalyst 5%, activator 3%, specific gravity 1.0t/m3Specific surface area 1.2m2G, porosity of 65%, physical strength ≧ 1000kg/cm2The water outlet of the micro-electrolysis reaction tower is connected with the water inlet of the adjusting pool;
the wastewater in the adjusting tank enters an inclined tube efficient sedimentation tank for mud-water separation, and the supernatant is pressurized to a hydrolysis acidification unit by a pump;
the hydrolysis acidification unit adopts combined type baffling board reactor type, the built-in vertical guide plate of reactor, separate into the reaction chamber of a plurality of series connections with the reactor, every reaction chamber all is a relatively independent upflow mud bed system, waste water rivers are turned over the flow and are advanced by the guide plate guide from top to bottom, pass through the mud bed in the reaction chamber one by one, the substrate in the aquatic fully contacts with the microorganism, the quantity of reaction chamber is 6 ~ 8, the aspect ratio of the upflow chamber of reactor along rivers direction of advance is at 1: 1-1: 2, the aspect ratio is 1: 3, erecting a semi-soft plastic fiber filler in the upper space of the reaction chamber, arranging a sludge discharge perforated pipe in the middle of the reactor, arranging a slag discharge pipe at the bottom of the reactor, and connecting a water outlet of the hydrolysis acidification unit with a water inlet of the anaerobic reactor;
the anaerobic reactor adopts a carbon steel anti-corrosion tower structure, and the volume load is 4-10 kgCOD/m3D, ascending flow rate: 0.9-1.1m/h, head loss: 0.76m, the pH value of the sewage entering the anaerobic reactor is between 6.5 and 8, the tower body is heated and insulated to control the water temperature to be 30 ℃, polyurethane filler is adopted, water is distributed by a perforated pipe, the diameter of a water distribution hole is phi 15mm, and the service area of each hole is 1 to 2m2The water outlet of the anaerobic reactor is connected with the water inlet of the high-load aerobic tank;
the combined filler is suspended in the high-load aerobic tank, the surface of the filler is full of a biological membrane, the filling rate is 70 percent, and the volume load of the filler is 0.5-3.0 kgBOD/m3D, filling 3-6 mg/L of dissolved oxygen in the tank, supplying air into water through an air blower and a microporous disc aerator, wherein the air-water ratio is 40-100: 1, and separating sludge and water from the effluent of the high-load aerobic tank through an inclined plate sedimentation tank and then feeding the effluent into a P-MBR deep aerobic biochemical section;
the P-MBR deep aerobic biochemical section removes refractory organic matters in the wastewater through biological metabolism of activated sludge and adsorption of active fillers, wherein the microbial biomass is more than 10g/L, and the gas-water ratio is as follows: 20:1, membrane flux: 13-15L/m2H, the particle size of the active filler is 100um, and the pore size of the membrane is 0.04 um.
The invention provides a method and a system for treating high-concentration refractory pharmaceutical wastewater. The process is provided with a pretreatment section and a biological reaction section, the front section and the rear section are inseparable and related, and the pretreatment section adopts a double-electric process of an electrolytic cell and a micro-electrolysis reaction tower; the biological section adopts 'hydrolytic acidification + anaerobic reactor + high-load aerobic + P-MBR deep aerobic biochemical treatment'.
The method has the advantages that the pharmaceutical wastewater is pretreated through the electrolytic cell and micro-electrolysis double-electric process, the pollutants which are difficult to degrade are partially decomposed and partially and directly degraded, toxic substances are removed, and a foundation is laid for biological reaction;
most pollutants are removed through hydrolytic acidification, anaerobic treatment and high-load aerobic treatment;
the application can decompose the pollutants which are stable in the pharmaceutical wastewater and not easy to degrade through the deep aerobic biochemical treatment of the P-MBR, and meet the higher water outlet requirement.
Compared with the prior art, the method and the system for treating the high-concentration refractory pharmaceutical wastewater achieve the following effects:
the application aims at the pharmaceutical wastewater which is difficult to degrade, and proper pretreatment is needed before biological reaction, so that the concentration of organic matters is reduced, and toxic and harmful substances are removed. The double-electric process is adopted, the operation and management are convenient, a large amount of medicaments such as hydrogen peroxide, ferrite and the like are not required to be added, and the labor intensity is reduced. The process is easy to be implemented, small in occupied area, free from the influence of external conditions and high in treatment effect
The fruit is stable.
The P-MBR technology of deep aerobic biochemical treatment has high reliability and stability, and is suitable for treating industrial wastewater which has high organic matter content, poor biodegradability, large water quality fluctuation and contains toxic and harmful substances. Under the conditions that the content of pollutants is reduced after the traditional biochemical treatment, the residual pollutants are stable in property and not easy to degrade, and meanwhile, the effluent water has high requirement, the P-MBR is adopted in the application, so that the retention time of the pollutants can be prolonged, stubborn COD (chemical oxygen demand) is removed, the influence of toxic and harmful substances is reduced, the impact resistance is strong, the flexibility is high, and good effects of color removal and deodorization are achieved.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is a flow chart of the method for treating high concentration refractory pharmaceutical wastewater of example 1.
Detailed Description
As used in the specification and in the claims, certain terms are used to refer to particular components. As one skilled in the art will appreciate, manufacturers may refer to a component by different names. This specification and claims do not intend to distinguish between components that differ in name but not function. In the following description and in the claims, the terms "include" and "comprise" are used in an open-ended fashion, and thus should be interpreted to mean "include, but not limited to. "substantially" means within an acceptable error range, and a person skilled in the art can solve the technical problem within a certain error range to substantially achieve the technical effect. Furthermore, the term "coupled" is intended to encompass any direct or indirect electrical coupling. Thus, if a first device couples to a second device, that connection may be through a direct electrical coupling or through an indirect electrical coupling via other devices and couplings. The following description is of the preferred embodiment for carrying out the invention, and is made for the purpose of illustrating the general principles of the invention and not for the purpose of limiting the scope of the invention. The scope of the present invention is defined by the appended claims.
The present invention will be described in further detail below with reference to the accompanying drawings, but the present invention is not limited thereto.
Example 1:
with reference to fig. 1, this embodiment provides a method for treating high-concentration refractory pharmaceutical wastewater, which includes the following steps:
step 1), high-concentration degradation-resistant pharmaceutical wastewater enters an adjusting tank to be mixed and adjusted in water quantity and water quality: the retention time in the regulating tank is 12-24 hours, the pH is regulated to be 4-7, and the mixture enters an electrolytic tank after being regulated;
high concentration pharmacy waste water is through mechanical gyration grid interception suspended solid and the bold floater in the waste water, prevents to block up pipeline and water pump, gets into the equalizing basin, and the equalizing basin dwell time sets for 12 ~ 24h, and the water yield and the abundant mixed regulation of quality of water to the waste water as far as possible reduce the impact of water mass to the system. Set up dive mixer in the pond and stir, prevent to deposit the corruption, do not adopt aeration mixing system, prevent that the poisonous gas in the waste water from spilling over the polluted environment. And adjusting the pH value to 4-7, and feeding the mixture into an electrolytic cell.
Step 2) carrying out electrolysis in an electrolytic cell: the electrolytic cell adopts a Ti-based PbO 2 coating electrode as an anode, a stainless steel electrode is used as a cathode, heavy metals in the wastewater are electrodeposited, the electrolysis time is 4 hours, the voltage is 4V, the current is 4-6A, the COD removal rate is 30-45%, cyanides and heavy metals such as copper, lead and zinc are removed, and the wastewater enters a micro-electrolysis reaction tower after being electrolyzed;
the electrolytic cell converts electric energy into chemical energy by utilizing an electrochemical principle, carries out oxidation and reduction reactions on organic or inorganic pollutants in the wastewater, utilizes higher electrocatalytic activity of an electrode in electrolysis of an aqueous solution, and adopts a high-frequency pulse power supply to decompose a hydroxyl radical ion strong oxidizer, thereby having good removal effect on organic matters, sulfides, cyanides and the like. The electrolytic cell adopts a Ti-based PbO 2 coating electrode as an anode, and the material of the electrolytic cell generally has the characteristics of good electrocatalytic activity, higher oxygen evolution overpotential, strong oxidizing ability, good corrosion resistance, good electrical conductivity, large current passing and the like; the cathode uses a stainless steel electrode to electrodeposit heavy metals. The electrolysis time is selected to be 4h, the voltage is 4V, the current is 4-6A, the COD removal rate can reach 30-45 percent, and the COD removal rate can be adjusted to
Removing heavy metals such as cyanide, copper, lead, zinc and the like.
Step 3) carrying out micro-electrolysis reaction in a micro-electrolysis reaction tower; the method comprises the following steps that the waste water stays in a micro-electrolysis reaction tower for 3-5 hours, iron-carbon efficient filler is filled in the micro-electrolysis reaction tower, the filler is sintered at 1300 ℃, and the filler comprises the following chemical components: refined iron powder not less than 75%, carbon content 17%, catalyst 5%, activator 3%, specific gravity 1.0t/m3Specific surface area 1.2m2G, porosity of 65%, physical strength ≧ 1000kg/cm2；
A micro-electrolysis reaction tower is arranged behind the electrolytic cell, and the iron and carbon in the high-efficiency filler have 1.2V potential difference to form a non-electrolyticSeveral micro-batteries, forming an electric field in the action space, generating a new ecology [ H ] in the process of wastewater treatment]Fe 2+ and the like can generate oxidation-reduction reaction with a plurality of components in the wastewater, such as breaking molecular chains, destroying chromophoric groups or chromophoric groups of colored substances in the wastewater, and achieving the effects of degradation and decoloration. The waste water stays in the micro-electrolysis reaction tower for 3-5 hours, most of reactors in the prior art are filled with scrap iron and sawdust, although the cost is low, the efficiency is not high, and hardening is easy, so that the invention selects the iron-carbon filled high-efficiency filler, the filler is processed by a 1300-degree sintering technology, and the chemical components are as follows: the content of refined iron powder is more than or equal to 75 percent, the content of carbon is approximately equal to 17 percent, the content of catalyst is approximately equal to 5 percent, and the content of activator is approximately equal to 3 percent. The technical parameters are as follows: specific weight of 1.0 ton/cubic meter, specific surface area of 1.2 square meter/g, porosity of 65%, and physical strength ≧ 1000KG/CM2. Wastewater enters from the bottom of the reactor and is uniformly distributed, and an on-line pH monitoring and adjusting system is arranged in the middle of the reactor because the alkalinity is gradually increased in the micro-electrolysis process, so that the inside of the reactor is always in a proper pH range.
And aerating the reactor, wherein the gas-water ratio is controlled to be about 3:1, and the water surface is boiled. In the micro-electrolysis reaction tower, organic substances which are difficult to remove and degrade and have structures of fluorine, carbon double bonds, nitryl, halogenated groups and the like can be degraded, fused rings and heterocyclic conjugated structures taking benzene rings as cores are broken, long-chain molecules are cut into short chains, and the B/C ratio is improved.
After the double electric action of the electrolytic cell and the micro-electrolysis, partial organic matters and chromaticity can be directly degraded, harmful substances can be converted into harmless substances, substances which are difficult to biodegrade are converted into substances which are easy to biodegrade and utilize, conditions are created for biological reaction, and the substances are used as a pretreatment process of biological treatment and are beneficial to sludge sedimentation and biofilm formation.
Step 4) adding a coagulant and a flocculant into the adjusting tank: adjusting the pH of effluent after micro-electrolysis reaction to 6-8, adding 30-50 mg/l of coagulant PFS and 5mg/l of flocculant PAM into the wastewater, reacting with suspended matters in the wastewater for 15-20 min, entering an inclined tube efficient sedimentation tank for mud-water separation, and pressurizing supernatant to a hydrolysis acidification unit by a pump;
the microelectrolysis effluent contains original ecological ferrous or ferric ions, has better coagulation effect than a common coagulant, the pH of the effluent is adjusted to 6-8, the coagulant PFS 30-50 mg/l and the flocculant PAM5mg/l are added into the wastewater in a supplementing manner, the mixture reacts with suspended matters in the wastewater for 15-20 min, and the mixture enters an inclined tube efficient sedimentation tank for mud-water separation. The supernatant is pressurized to a hydrolysis acidification unit by a pump.
Step 5) processing in a hydrolysis acidification unit: hydrolysis acidification unit is anaerobic environment, dwell time 10h, adopt combined type baffling board reactor type among this hydrolysis acidification unit, the built-in vertical guide plate of reactor, separate into the reactor a plurality of reaction chambers of establishing ties, every reaction chamber all is a relatively independent upflow mud bed system, waste water rivers are advanced by baffle guide upper and lower baffling, pass through the mud bed in the reaction chamber one by one, the substrate in the aquatic fully contacts with the microorganism, the quantity of reaction chamber is 6 ~ 8, the aspect ratio of the upflow room along rivers advancing direction of reactor is at 1: 1-1: 2, the aspect ratio is 1: 3, erecting a semi-soft plastic fiber filler in the upper space of the reaction chamber, arranging a sludge discharge perforated pipe in the middle of the reactor, arranging a slag discharge pipe at the bottom of the reactor, and feeding the effluent of the hydrolysis acidification unit into an anaerobic reactor;
the hydrolytic acidification unit can continuously improve the biodegradability of the wastewater, convert insoluble organic matters into soluble organic matters and improve the treatment effect of subsequent biological units. The hydrolysis acidification unit is in strict anaerobic environment, the retention time is 10 hours, the anaerobic treatment is controlled in the first stage and the second stage of anaerobic treatment with short reaction time, namely, insoluble organic matters are hydrolyzed into soluble organic matters under the action of a large amount of hydrolytic bacteria and acidifying bacteria. A composite baffle plate reactor (HABR) is adopted, and a high-efficiency anaerobic biological treatment device is developed and developed on the basis of summarizing the process performance of a second-generation anaerobic reactor by adopting the baffle plate reactor. The reactor is characterized in that a vertical guide plate is arranged in the reactor to divide the reactor into a plurality of reaction chambers connected in series, each reaction chamber is a relatively independent upflow sludge bed system, and sludge exists in a granular form or a flocculent form. The water flow is guided by the guide plate to flow upwards and downwards in a baffling way and passes through the sludge bed layers in the reaction chamber one by one, and the substrates in the inlet water are fully contacted with the microorganisms to be degraded and removed. The number of the compartments is 6-8, and the length-width ratio of the upstream chamber of the reactor along the advancing direction of water flow is preferably controlled to be 1: 1-1: 2, the aspect ratio is generally 1: 3 the semi-soft plastic fiber filler is erected in the upper space of the reaction chamber, the total amount of organisms is increased by utilizing the original invalid volume, and in addition, the separation of sludge and bubbles is accelerated, so that the loss of the sludge is reduced. The middle part of the reactor is provided with a sludge discharge perforated pipe, and the bottom part of the reactor is provided with a slag discharge pipe. The B/C ratio can be improved to more than 0.35 by hydrolysis acidification, and the COD removal rate reaches about 30 percent.
Step 6) carrying out anaerobic reaction in an anaerobic reactor: the anaerobic reactor adopts a carbon steel anti-corrosion tower structure, and the volume load is 4-10 kgCOD/m3D, ascending flow rate: 0.9-1.1m/h, head loss: 0.76m, the pH value of the sewage entering the anaerobic reactor is between 6.5 and 8, the tower body is heated and insulated to control the water temperature to be 30 ℃, polyurethane filler is adopted, water is distributed by a perforated pipe, the diameter of a water distribution hole is phi 15mm, and the service area of each hole is 1 to 2m2The water is discharged from the open channel, and the water discharged from the anaerobic reactor enters a high-load aerobic tank;
the effluent of the hydrolysis acidification unit enters an anaerobic reactor, organic matters in the wastewater are finally degraded into substances such as methane, hydrogen, carbon dioxide and the like under a strictly controlled anaerobic environment, and the anaerobic reactor adopts an up-flow anaerobic filter bed (UBF). The UBF mainly comprises a water distributor, a sludge layer and a packing layer, wherein the sludge bed consisting of high-concentration granular sludge is arranged below the UBF, the packing layer consisting of packing and biomembranes attached to the packing layer is arranged at the upper part of the UBF, and the UBF is filled at the 1/3 volume part at the upper part of the reactor. The soft filler in the equipment is used as a fluidization carrier. The sewage is used as a flowing medium, anaerobic microorganisms are bonded on the surface of the soft filler in a biofilm mode, and the anaerobic microorganisms are automatically mixed when methane gas is generated in a circulating pump or a sewage treatment process, so that the sewage is in a flowing state. The UBF composite anaerobic fluidized bed has the advantages of high efficiency, small occupied area and suitability for high-concentration and difficult-degradation organic sewage treatment engineering. The reactor adopts a carbon steel anti-corrosion tower structure, and the volume load is 4-10 kgCOD/m3D, ascending flow rate: 0.9-1.1m/h, head loss: 0.76 m. The pH value of the raw sewage entering the anaerobic reactor is controlled to be about 6.5-8, and the tower body is heated and insulated to ensure that the water temperature is controlled to be 30 ℃. Adopting polyurethane fillingThe material and the water are distributed by a perforated pipe, the diameter of the water distribution hole is phi 15mm, and the service area of each hole is 1-2 m2And discharging water from the open channel.
The removal rate of COD can reach 50-70%.
Step 7) carrying out aerobic reaction in a high-load aerobic tank: the combined filler is suspended in the high-load aerobic tank, the surface of the filler is full of a biological membrane, the filling rate is 70 percent, and the volume load of the filler is 0.5-3.0 kgBOD/m3D, filling 3-6 mg/L of dissolved oxygen in the tank, supplying air into water through an air blower and a microporous disc aerator, wherein the air-water ratio is 40-100: 1, performing aerobic reaction in a high-load aerobic tank, performing sludge-water separation in an inclined plate sedimentation tank, and then entering a P-MBR deep aerobic biochemical section;
the effluent enters a high-load aerobic section after passing through the anaerobic unit, and has higher sludge load and strong impact load resistance under the conditions of high influent water concentration and large water quality and water quantity change. The combined filler is suspended in the tank, the surface of the filler is full of the biological membrane, the filling rate is 70 percent, and the volume load of the filler is 0.5-3.0 kgBOD/m3D, filling the pool with dissolved oxygen of 3-6 mg/L, and supplying air to the water through a blower and a microporous disc aerator, wherein the ratio of air to water is 40-100: 1. After passing through the high-load aerobic section, the concentration of organic matters is reduced to below 1000 ppm. And carrying out sludge-water separation in a high-efficiency inclined plate sedimentation tank, and then entering a P-MBR deep aerobic biochemical section.
Step 8) carrying out deep aerobic reaction in the P-MBR deep aerobic biochemical section: in the P-MBR deep aerobic biochemical section, refractory organic matters in the wastewater are removed through biological metabolism of activated sludge and adsorption of active fillers, wherein the microbial biomass is more than 10g/L, and the gas-water ratio is as follows: 20:1, membrane flux: 13-15L/m2H, the particle size of the active filler is 100um, the pore diameter of the membrane is 0.04um, and the treated wastewater can be discharged.
And (3) further removing residual refractory organic matters in the water by using special bacteria in a P-MBR deep aerobic biochemical section through the biological metabolism of activated sludge and the adsorption effect of active fillers. The water power retention time of the pollutants in the reaction tank is changed into solid retention time through the adsorption effect of the active filler, so that the reaction time is prolonged, and the treatment purpose is achieved. The interception of the membrane and the adsorption of the active filler are utilized to keep the concentration of the microorganism specially used for treating the refractory organic matters, thereby ensuring the effluent effect. The COD of the effluent after the treatment of the system can be stabilized below 50.
The adsorption effect of the active filler and the interception effect of the membrane can ensure the existence of the special bacteria generated by the system, and the special bacteria cannot be lost along with water, so that the quantity of the special bacteria in the reaction tank is ensured; due to the strong adsorption effect of the active filler, pollutants in the incoming water are adsorbed on the active filler and cannot flow out along with the water, and can flow back into the biochemical reaction tank for reaction through sludge backflow, so that the hydraulic retention time of the pollutants in the traditional biochemical reaction process can be converted into the solid retention time, and the pollutants can be biochemically degraded in a limited hydraulic time condition; due to the interception of the membrane and the adsorption effect of the active filler, even if filamentous bacteria causing sludge expansion are generated in the biochemical reaction tank, the sludge can not be lost;
as the active filler adsorbs pollutants on the filler, the part of pollutants which can not be subjected to biochemical degradation can not flow out along with water, and can be discharged as sludge together with the active filler and residual sludge, thereby ensuring the quality of the effluent. In addition, the particle size of the active filler is about 100um, the pore diameter of the membrane is about 0.04um, compared with the membrane pores and the finely-divided zoogloea, the active filler and the bacteria adsorbed by the active filler are not easy to remain in the membrane filaments and are easy to remove by scrubbing the membrane;
and the volume difference formed between the active filler with larger volume and the smaller zoogloea is beneficial to preventing the blockage of the membrane and removing the fouling and blocking substances on the surface of the membrane, so that the flux of the membrane can be improved, the cleaning times of the membrane can be reduced, and the service life of the membrane can be prolonged.
The aerobic section of the P-MBR has high-concentration microorganism amount which can reach more than 10 g/L. Gas-water ratio: 20:1. Membrane flux: correspondingly, the embodiment also discloses a high-concentration degradation-resistant pharmaceutical wastewater treatment system, which comprises an adjusting tank, an electrolytic tank, a micro-electrolysis reaction tower, an adjusting tank, a hydrolysis acidification unit, an anaerobic reactor, a high-load aerobic tank and a P-MBR deep aerobic biochemical section which are connected in sequence, wherein,
the adjusting tank is used for mixing and adjusting the water quantity and the water quality of the wastewater, the pH value in the adjusting tank is 4-7, and a water outlet of the adjusting tank is connected with a water inlet of the electrolytic tank;
the electrolytic cell adopts a Ti-based PbO 2 coating electrode as an anode, a stainless steel electrode as a cathode, heavy metals in the wastewater are electrodeposited, the electrolysis time is 4h, the voltage is 4V, the current is 4-6A, and a water outlet of the electrolytic cell is connected with a water inlet of the micro-electrolysis reaction tower;
the micro-electrolysis reaction tower is filled with iron-carbon efficient filler, the filler is sintered at 1300 ℃, and the filler comprises the following chemical components: refined iron powder not less than 75%, carbon content 17%, catalyst 5%, activator 3%, specific gravity 1.0t/m3Specific surface area 1.2m2G, porosity of 65%, physical strength ≧ 1000kg/cm2The water outlet of the micro-electrolysis reaction tower is connected with the water inlet of the adjusting pool;
the wastewater in the adjusting tank enters an inclined tube efficient sedimentation tank for mud-water separation, and the supernatant is pressurized to a hydrolysis acidification unit by a pump;
the hydrolysis acidification unit adopts combined type baffling board reactor type, the built-in vertical guide plate of reactor, separate into the reaction chamber of a plurality of series connections with the reactor, every reaction chamber all is a relatively independent upflow mud bed system, waste water rivers are turned over the flow and are advanced by the guide plate guide from top to bottom, pass through the mud bed in the reaction chamber one by one, the substrate in the aquatic fully contacts with the microorganism, the quantity of reaction chamber is 6 ~ 8, the aspect ratio of the upflow chamber of reactor along rivers direction of advance is at 1: 1-1: 2, the aspect ratio is 1: 3, erecting a semi-soft plastic fiber filler in the upper space of the reaction chamber, arranging a sludge discharge perforated pipe in the middle of the reactor, arranging a slag discharge pipe at the bottom of the reactor, and connecting a water outlet of the hydrolysis acidification unit with a water inlet of the anaerobic reactor;
the anaerobic reactor adopts a carbon steel anti-corrosion tower structure, and the volume load is 4-10 kgCOD/m3D, ascending flow rate: 0.9-1.1m/h, head loss: 0.76 m. pH value of sewage entering anaerobic reactorBetween 6.5 and 8 ℃, the tower body is heated and insulated to control the water temperature at 30 ℃, polyurethane filler is adopted, water is distributed by a perforated pipe for water inlet, the diameter of a water distribution hole is phi 15mm, and the service area of each hole is 1 to 2m2The water outlet of the anaerobic reactor is connected with the water inlet of the high-load aerobic tank;
the combined filler is suspended in the high-load aerobic tank, the surface of the filler is full of a biological membrane, the filling rate is 70 percent, and the volume load of the filler is 0.5-3.0 kgBOD/m3D, filling 3-6 mg/L of dissolved oxygen in the tank, supplying air into water through an air blower and a microporous disc aerator, wherein the air-water ratio is 40-100: 1, and separating sludge and water from the effluent of the high-load aerobic tank through an inclined plate sedimentation tank and then feeding the effluent into a P-MBR deep aerobic biochemical section;
the P-MBR deep aerobic biochemical section removes refractory organic matters in the wastewater through biological metabolism of activated sludge and adsorption of active fillers, wherein the microbial biomass is more than 10g/L, and the gas-water ratio is as follows: 20:1, membrane flux: 13-15L/m2H, the particle size of the active filler is 100um, and the pore size of the membrane is 0.04 um.
Example 2:
the embodiment provides a method for treating high-concentration refractory pharmaceutical wastewater, which comprises the following steps:
step 1), high-concentration degradation-resistant pharmaceutical wastewater enters an adjusting tank to be mixed and adjusted in water quantity and water quality: the retention time in the regulating tank is 12h, the pH value is 4, and the regulated solution enters an electrolytic tank;
the high-concentration pharmaceutical wastewater is intercepted by the mechanical rotary grating to prevent the suspended matters and the large floating matters in the wastewater from blocking pipelines and water pumps and entering the regulating tank, so that the water quantity and the water quality of the wastewater are fully mixed and regulated as much as possible, and the impact of the water quality on a system is reduced. Set up dive mixer in the pond and stir, prevent to deposit the corruption, do not adopt aeration mixing system, prevent that the poisonous gas in the waste water from spilling over the polluted environment. After 12 hours of residence and adjustment of the pH4, the cell was charged.
Step 2) carrying out electrolysis in an electrolytic cell: the electrolytic cell adopts a Ti-based PbO 2 coating electrode as an anode, a stainless steel electrode is used as a cathode, heavy metals in the wastewater are electrodeposited, the electrolysis time is 4h, the voltage is 4V, the current is 4-6A, the COD removal rate is 32%, cyanides and heavy metals such as copper, lead and zinc are removed, and the wastewater enters a micro-electrolysis reaction tower after being electrolyzed;
step 3) carrying out micro-electrolysis reaction in a micro-electrolysis reaction tower; the method comprises the following steps that the waste water stays in a micro-electrolysis reaction tower for 3-5 hours, iron-carbon efficient filler is filled in the micro-electrolysis reaction tower, the filler is sintered at 1300 ℃, and the filler comprises the following chemical components: refined iron powder not less than 75%, carbon content 17%, catalyst 5%, activator 3%, specific gravity 1.0t/m3Specific surface area 1.2m2G, porosity of 65%, physical strength ≧ 1000kg/cm2；
After the double electric action of an electrolytic cell and micro-electrolysis, partial organic matters and chromaticity can be directly degraded, harmful substances can be converted into harmless substances, substances which are difficult to biodegrade are converted into substances which are easy to biodegrade and utilize, conditions are created for biological reaction, and the substances are used as a pretreatment process of biological treatment and are beneficial to sludge sedimentation and biological biofilm formation.
Step 4) adding a coagulant and a flocculant into the adjusting tank: adjusting the pH value of effluent after micro-electrolysis reaction to 6, supplementing and adding a coagulant PFS (PFS) 30mg/l and a flocculant PAM (polyacrylamide) 5mg/l into the wastewater, reacting with suspended matters in the wastewater for 15min, entering an inclined-tube efficient sedimentation tank for mud-water separation, and pressurizing supernatant to a hydrolysis acidification unit by a pump;
step 5) processing in a hydrolysis acidification unit: hydrolysis acidification unit is anaerobic environment, dwell time 10h, adopt combined type baffling board reactor type among this hydrolysis acidification unit, the built-in vertical guide plate of reactor, separate into the reactor a plurality of reaction chambers of establishing ties, every reaction chamber all is a relatively independent upflow mud bed system, waste water rivers are advanced by baffle guide upper and lower baffling, pass through the mud bed in the reaction chamber one by one, the substrate in the aquatic fully contacts with the microorganism, the quantity of reaction chamber is 6, the aspect ratio of the upflow room along rivers advancing direction of reactor is at 1: 1, the aspect ratio is 1: 3, erecting a semi-soft plastic fiber filler in the upper space of the reaction chamber, arranging a sludge discharge perforated pipe in the middle of the reactor, arranging a slag discharge pipe at the bottom of the reactor, and feeding the effluent of the hydrolysis acidification unit into an anaerobic reactor;
the B/C ratio can be improved to more than 0.37 by hydrolysis acidification, and the COD removal rate reaches about 32 percent.
Step 6) carrying out anaerobic reaction in an anaerobic reactor: the anaerobic reactor adopts a carbon steel anti-corrosion tower structure, and the volume load is 10kgCOD/m3D, ascending flow rate: 1.1m/h, head loss: 0.76 m. The pH value of sewage entering the anaerobic reactor is 6.5-8, the tower body is heated and insulated to control the water temperature at 30 ℃, polyurethane filler is adopted, water is distributed by a perforated pipe for water inlet, the diameter of a water distribution hole is phi 15mm, and the service area of each hole is 1-2 m2The water is discharged from the open channel, and the water discharged from the anaerobic reactor enters a high-load aerobic tank;
in this example, the removal rate of COD in the anaerobic reaction reached 56%.
Step 7) carrying out aerobic reaction in a high-load aerobic tank: the combined filler is suspended in the high-load aerobic tank, the surface of the filler is full of a biological membrane, the filling rate is 70 percent, and the volume load of the filler is 0.5kgBOD/m3D, filling 3mg/L of dissolved oxygen in the tank, supplying air to water through an air blower and a microporous disc aerator, wherein the air-water ratio is 40:1, carrying out aerobic reaction in a high-load aerobic tank, carrying out sludge-water separation in an inclined plate sedimentation tank, and then entering a P-MBR deep aerobic biochemical section;
after passing through the high-load aerobic section, the concentration of organic matters is reduced to below 1000 ppm. And carrying out sludge-water separation in a high-efficiency inclined plate sedimentation tank, and then entering a P-MBR deep aerobic biochemical section.
Step 8) carrying out deep aerobic reaction in the P-MBR deep aerobic biochemical section: in the P-MBR deep aerobic biochemical section, refractory organic matters in the wastewater are removed through biological metabolism of activated sludge and adsorption of active fillers, wherein the microbial biomass is more than 10g/L, and the gas-water ratio is as follows: 20:1, membrane flux: 13L/m2H, the particle size of the active filler is 100um, the pore diameter of the membrane is 0.04um, and the treated wastewater can be discharged.
The COD of the effluent after the treatment of the system is stabilized below 49.
Example 3:
the embodiment provides a method for treating high-concentration refractory pharmaceutical wastewater, which comprises the following steps:
step 1), high-concentration degradation-resistant pharmaceutical wastewater enters an adjusting tank to be mixed and adjusted in water quantity and water quality: the retention time in the regulating tank is 24 hours, the pH value is 7, and the regulated solution enters the electrolytic tank;
step 2) carrying out electrolysis in an electrolytic cell: in the electrolytic cell, a Ti-based PbO 2 coating electrode is used as an anode, a stainless steel electrode is used as a cathode, heavy metals in wastewater are electrodeposited, the electrolytic time is 4h, the voltage is 4V, the current is 6A, the COD removal rate can reach 45%, cyanides and heavy metals such as copper, lead and zinc are removed, and the obtained product enters a micro-electrolysis reaction tower after electrolysis;
step 3) carrying out micro-electrolysis reaction in a micro-electrolysis reaction tower; the method comprises the following steps that the waste water stays in a micro-electrolysis reaction tower for 3-5 hours, iron-carbon efficient filler is filled in the micro-electrolysis reaction tower, the filler is sintered at 1300 ℃, and the filler comprises the following chemical components: refined iron powder not less than 75%, carbon content 17%, catalyst 5%, activator 3%, specific gravity 1.0t/m3Specific surface area 1.2m2G, porosity of 65%, physical strength ≧ 1000kg/cm2；
After the double electric action of an electrolytic cell and micro-electrolysis, partial organic matters and chromaticity can be directly degraded, harmful substances can be converted into harmless substances, substances which are difficult to biodegrade are converted into substances which are easy to biodegrade and utilize, conditions are created for biological reaction, and the substances are used as a pretreatment process of biological treatment and are beneficial to sludge sedimentation and biological biofilm formation.
Step 4) adding a coagulant and a flocculant into the adjusting tank: adjusting the pH value of effluent after micro-electrolysis reaction to 8, adding 50mg/l of coagulant PFS and 5mg/l of flocculant PAM into the wastewater, reacting with suspended matters in the wastewater for 20min, entering an inclined tube high-efficiency sedimentation tank for mud-water separation, and pressurizing supernatant to a hydrolysis acidification unit by a pump;
step 5) processing in a hydrolysis acidification unit: hydrolysis acidification unit is anaerobic environment, dwell time 10h, adopt combined type baffling board reactor type among this hydrolysis acidification unit, the built-in vertical guide plate of reactor, separate into the reactor a plurality of reaction chambers of establishing ties, every reaction chamber all is a relatively independent upflow mud bed system, waste water rivers are advanced by baffle guide upper and lower baffling, pass through the mud bed in the reaction chamber one by one, the substrate in the aquatic fully contacts with the microorganism, the quantity of reaction chamber is 8, the aspect ratio of the upflow room along rivers advancing direction of reactor is at 1: 2, the aspect ratio is 1: 3, erecting a semi-soft plastic fiber filler in the upper space of the reaction chamber, arranging a sludge discharge perforated pipe in the middle of the reactor, arranging a slag discharge pipe at the bottom of the reactor, and feeding the effluent of the hydrolysis acidification unit into an anaerobic reactor;
the B/C ratio can be improved to 0.38 by hydrolysis acidification, and the COD removal rate can reach about 35 percent.
Step 6) carrying out anaerobic reaction in an anaerobic reactor: the anaerobic reactor adopts a carbon steel anti-corrosion tower structure, and the volume load is 10kgCOD/m3D, ascending flow rate: 1.1m/h, head loss: 0.76 m. The pH value of sewage entering an anaerobic reactor is 8, the tower body is heated and insulated to control the water temperature to be 30 ℃, polyurethane filler is adopted, water is distributed by a perforated pipe, the diameter of a water distribution hole is phi 15mm, and the service area of each hole is 1-2 m2The water is discharged from the open channel, and the water discharged from the anaerobic reactor enters a high-load aerobic tank;
the removal rate of COD can reach 70 percent.
Step 7) carrying out aerobic reaction in a high-load aerobic tank: the combined filler is suspended in the high-load aerobic tank, the surface of the filler is full of a biological membrane, the filling rate is 70 percent, and the volume load of the filler is 3.0kgBOD/m3D, filling 6mg/L of dissolved oxygen in the tank, supplying air to water through an air blower and a microporous disc aerator, wherein the air-water ratio is 100:1, carrying out aerobic reaction in a high-load aerobic tank, carrying out sludge-water separation in an inclined plate sedimentation tank, and then entering a P-MBR deep aerobic biochemical section;
after passing through the high-load aerobic section, the concentration of organic matters is reduced to below 1000 ppm. And carrying out sludge-water separation in a high-efficiency inclined plate sedimentation tank, and then entering a P-MBR deep aerobic biochemical section.
Step 8) carrying out deep aerobic reaction in the P-MBR deep aerobic biochemical section: in the P-MBR deep aerobic biochemical section, refractory organic matters in the wastewater are removed through biological metabolism of activated sludge and adsorption of active fillers, wherein the microbial biomass is more than 10g/L, and the gas-water ratio is as follows: 20:1, membrane flux: 13-15L/m2H, the particle size of the active filler is 100um, and the pore diameter of the membrane is 0.04um, the treated wastewater can be discharged.
The COD of the effluent after being treated by the system can be stabilized below 38.
Example 4:
the embodiment provides a method for treating high-concentration refractory pharmaceutical wastewater, which comprises the following steps:
step 1), high-concentration degradation-resistant pharmaceutical wastewater enters an adjusting tank to be mixed and adjusted in water quantity and water quality: the retention time in the regulating tank is 20 hours, the pH is regulated to be 4-7, and the mixture enters an electrolytic tank after being regulated;
step 2) carrying out electrolysis in an electrolytic cell: the electrolytic cell adopts a Ti-based PbO 2 coating electrode as an anode, a stainless steel electrode is used as a cathode, heavy metals in the wastewater are electrodeposited, the electrolytic time is 4 hours, the voltage is 4V, the current is 4-6A, the COD removal rate reaches 40%, and the heavy metals such as cyanide, copper, lead, zinc and the like can be removed, and the heavy metals enter a micro-electrolysis reaction tower after electrolysis;
step 3) carrying out micro-electrolysis reaction in a micro-electrolysis reaction tower; the method comprises the following steps that the waste water stays in a micro-electrolysis reaction tower for 3-5 hours, iron-carbon efficient filler is filled in the micro-electrolysis reaction tower, the filler is sintered at 1300 ℃, and the filler comprises the following chemical components: refined iron powder not less than 75%, carbon content 17%, catalyst 5%, activator 3%, specific gravity 1.0t/m3Specific surface area 1.2m2G, porosity of 65%, physical strength ≧ 1000kg/cm2；
After the double electric action of an electrolytic cell and micro-electrolysis, partial organic matters and chromaticity can be directly degraded, harmful substances can be converted into harmless substances, substances which are difficult to biodegrade are converted into substances which are easy to biodegrade and utilize, conditions are created for biological reaction, and the substances are used as a pretreatment process of biological treatment and are beneficial to sludge sedimentation and biological biofilm formation.
Step 4) adding a coagulant and a flocculant into the adjusting tank: adjusting the pH value of the effluent after the micro-electrolysis reaction to 7, supplementing and adding a coagulant PFS40mg/l and a flocculant PAM5mg/l into the wastewater, reacting with suspended matters in the wastewater for 17min, entering an inclined-tube efficient sedimentation tank for mud-water separation, and pressurizing the supernatant to a hydrolysis acidification unit by a pump;
step 5) processing in a hydrolysis acidification unit: hydrolysis acidification unit is anaerobic environment, dwell time 10h, adopt combined type baffling board reactor type among this hydrolysis acidification unit, the built-in vertical guide plate of reactor, separate into the reactor a plurality of reaction chambers of establishing ties, every reaction chamber all is a relatively independent upflow mud bed system, waste water rivers are advanced by baffle guide upper and lower baffling, pass through the mud bed in the reaction chamber one by one, the substrate in the aquatic fully contacts with the microorganism, the quantity of reaction chamber is 7, the aspect ratio of the upflow room along rivers advancing direction of reactor is at 1: 2, aspect ratio of 1: 3, erecting a semi-soft plastic fiber filler in the upper space of the reaction chamber, arranging a sludge discharge perforated pipe in the middle of the reactor, arranging a slag discharge pipe at the bottom of the reactor, and feeding the effluent of the hydrolysis acidification unit into an anaerobic reactor;
the B/C ratio can be improved to more than 0.35 by hydrolysis acidification, and the COD removal rate reaches about 31 percent.
Step 6) carrying out anaerobic reaction in an anaerobic reactor: the anaerobic reactor adopts a carbon steel anti-corrosion tower structure, and the volume load is 7kgCOD/m3D, ascending flow velocity of 1.0m/h, head loss of 0.76 m. The pH value of the sewage entering the anaerobic reactor is 7, the tower body is heated and insulated to control the water temperature at 30 ℃, polyurethane filler is adopted, the water is distributed by a perforated pipe, the diameter of a water distribution hole is phi 15mm, and the service area of each hole is 1.5m2The water is discharged from the open channel, and the water discharged from the anaerobic reactor enters a high-load aerobic tank;
the removal rate of COD reaches 60 percent.
Step 7) carrying out aerobic reaction in a high-load aerobic tank: the combined filler is suspended in the high-load aerobic tank, the surface of the filler is full of a biological membrane, the filling rate is 70 percent, and the volume load of the filler is 1.8kgBOD/m3D, filling 4mg/L of dissolved oxygen in the tank, supplying air to the water through an air blower and a microporous disc aerator, wherein the air-water ratio is 70:1, carrying out aerobic reaction in a high-load aerobic tank, carrying out sludge-water separation in an inclined plate sedimentation tank, and then entering a P-MBR deep aerobic biochemical section;
after passing through the high-load aerobic section, the concentration of organic matters is reduced to below 1000 ppm. And carrying out sludge-water separation in a high-efficiency inclined plate sedimentation tank, and then entering a P-MBR deep aerobic biochemical section.
Step (ii) of8) Carrying out deep aerobic reaction in a P-MBR deep aerobic biochemical section: in the P-MBR deep aerobic biochemical section, refractory organic matters in the wastewater are removed through biological metabolism of activated sludge and adsorption of active fillers, wherein the microbial biomass is more than 10g/L, and the gas-water ratio is as follows: 20:1, membrane flux 14L/m2H, the particle size of the active filler is 100um, the pore diameter of the membrane is 0.04um, and the treated wastewater can be discharged.
The COD of the effluent after the treatment of the system can be stabilized below 40.
Compared with the prior art, the method and the system for treating the high-concentration refractory pharmaceutical wastewater achieve the following effects:
the application aims at the pharmaceutical wastewater which is difficult to degrade, and proper pretreatment is needed before biological reaction, so that the concentration of organic matters is reduced, and toxic and harmful substances are removed. The double-electric process is adopted, the operation and management are convenient, a large amount of medicaments such as hydrogen peroxide, ferrite and the like are not required to be added, and the labor intensity is reduced. The process is easy to implement, small in occupied area, free from the influence of external conditions and stable in treatment effect.
The foregoing description shows and describes several preferred embodiments of the invention, but as aforementioned, it is to be understood that the invention is not limited to the forms disclosed herein, but is not to be construed as excluding other embodiments and is capable of use in various other combinations, modifications, and environments and is capable of changes within the scope of the inventive concept as expressed herein, commensurate with the above teachings, or the skill or knowledge of the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (2)

1. A method for treating high-concentration refractory pharmaceutical wastewater is characterized by comprising the following steps:
step 1), high-concentration degradation-resistant pharmaceutical wastewater enters an adjusting tank to be mixed and adjusted in water quantity and water quality: the retention time in the regulating tank is 12-24 hours, the pH is regulated to be 4-7, and the mixture enters an electrolytic tank after being regulated;
step 2) carrying out electrolysis in an electrolytic cell: the electrolytic cell adopts Ti basePbO2A plating electrode is used as an anode, a stainless steel electrode is used as a cathode, heavy metals in the wastewater are electrodeposited, the electrolysis time is 4h, the voltage is 4V, the current is 4-6A, the COD removal rate is 30-45%, cyanides, heavy metals such as copper, lead and zinc are removed, and the wastewater enters a micro-electrolysis reaction tower after being electrolyzed;
step 3) carrying out micro-electrolysis reaction in a micro-electrolysis reaction tower; the method comprises the following steps that the waste water stays in a micro-electrolysis reaction tower for 3-5 hours, iron-carbon efficient filler is filled in the micro-electrolysis reaction tower, the filler is sintered at 1300 ℃, and the filler comprises the following chemical components: refined iron powder not less than 75%, carbon content 17%, catalyst 5%, activator 3%, specific gravity 1.0t/m3Specific surface area 1.2m2G, porosity of 65%, physical strength ≧ 1000kg/cm2；
Step 4) adding a coagulant and a flocculant into the adjusting tank: adjusting the pH of effluent after micro-electrolysis reaction to 6-8, adding 30-50 mg/l of coagulant PFS and 5mg/l of flocculant PAM into the wastewater, reacting with suspended matters in the wastewater for 15-20 min, entering an inclined tube efficient sedimentation tank for mud-water separation, and pressurizing supernatant to a hydrolysis acidification unit by a pump;
step 5) processing in a hydrolysis acidification unit: hydrolysis acidification unit is anaerobic environment, dwell time 10h, adopt combined type baffling board reactor type among this hydrolysis acidification unit, the built-in vertical guide plate of reactor, separate into the reactor a plurality of reaction chambers of establishing ties, every reaction chamber all is a relatively independent upflow mud bed system, waste water rivers are advanced by baffle guide upper and lower baffling, pass through the mud bed in the reaction chamber one by one, the substrate in the aquatic fully contacts with the microorganism, the quantity of reaction chamber is 6 ~ 8, the aspect ratio of the upflow room along rivers advancing direction of reactor is at 1: 1-1: 2, the aspect ratio is 1: 3, erecting a semi-soft plastic fiber filler in the upper space of the reaction chamber, arranging a sludge discharge perforated pipe in the middle of the reactor, arranging a slag discharge pipe at the bottom of the reactor, and feeding the effluent of the hydrolysis acidification unit into an anaerobic reactor;
step 6) carrying out anaerobic reaction in an anaerobic reactor: the anaerobic reactor adopts a carbon steel anti-corrosion tower structure, and the volume load is 4-10 kgCOD/m3D, ascending flow rate: 0.9-1.1m/h, waterHead loss: 0.76m, the pH value of the sewage entering the anaerobic reactor is between 6.5 and 8, the tower body is heated and insulated to control the water temperature to be 30 ℃, polyurethane filler is adopted, water is distributed by a perforated pipe, the diameter of a water distribution hole is phi 15mm, and the service area of each hole is 1 to 2m2The water is discharged from the open channel, and the water discharged from the anaerobic reactor enters a high-load aerobic tank;
step 7) carrying out aerobic reaction in a high-load aerobic tank: the combined filler is suspended in the high-load aerobic tank, the surface of the filler is full of a biological membrane, the filling rate is 70 percent, and the volume load of the filler is 0.5-3.0 kgBOD/m3D, filling 3-6 mg/L of dissolved oxygen in the tank, supplying air into water through an air blower and a microporous disc aerator, wherein the air-water ratio is 40-100: 1, performing aerobic reaction in a high-load aerobic tank, performing sludge-water separation in an inclined plate sedimentation tank, and then entering a P-MBR deep aerobic biochemical section;
step 8) carrying out deep aerobic reaction in the P-MBR deep aerobic biochemical section: in the P-MBR deep aerobic biochemical section, refractory organic matters in the wastewater are removed through biological metabolism of activated sludge and adsorption of active fillers, wherein the microbial biomass is more than 10g/L, and the gas-water ratio is as follows: 20:1, membrane flux: 13-15L/m2H, the particle size of the active filler is 100um, the pore diameter of the membrane is 0.04um, and the treated wastewater can be discharged.
2. The high-concentration degradation-resistant pharmaceutical wastewater treatment system is characterized by comprising an adjusting tank, an electrolytic tank, a micro-electrolysis reaction tower, an adjusting tank, a hydrolysis acidification unit, an anaerobic reactor, a high-load aerobic tank and a P-MBR deep aerobic biochemical section which are connected in sequence, wherein the adjusting tank is used for mixing and adjusting the water quantity and the water quality of wastewater, the pH value in the adjusting tank is 4-7, and the water outlet of the adjusting tank is connected with the water inlet of the electrolytic tank;
the electrolytic cell adopts Ti-based PbO2The plating electrode is used as an anode, a stainless steel electrode is used as a cathode, heavy metals in the wastewater are electrodeposited, the electrolysis time is 4 hours, the voltage is 4V, the current is 4-6A, and the water outlet of the electrolytic cell is connected with the water inlet of the micro-electrolysis reaction tower;
the micro-electrolysis reaction tower is filled with iron-carbon efficient fillerThe filler is sintered at 1300 ℃, and the chemical components of the filler are as follows: refined iron powder not less than 75%, carbon content 17%, catalyst 5%, activator 3%, specific gravity 1.0t/m3Specific surface area 1.2m2G, porosity of 65%, physical strength ≧ 1000kg/cm2The water outlet of the micro-electrolysis reaction tower is connected with the water inlet of the adjusting pool;
the wastewater in the adjusting tank enters an inclined tube efficient sedimentation tank for mud-water separation, and the supernatant is pressurized to a hydrolysis acidification unit by a pump;
the hydrolysis acidification unit adopts combined type baffling board reactor type, the built-in vertical guide plate of reactor, separate into the reaction chamber of a plurality of series connections with the reactor, every reaction chamber all is a relatively independent upflow mud bed system, waste water rivers are turned over the flow and are advanced by the guide plate guide from top to bottom, pass through the mud bed in the reaction chamber one by one, the substrate in the aquatic fully contacts with the microorganism, the quantity of reaction chamber is 6 ~ 8, the aspect ratio of the upflow chamber of reactor along rivers direction of advance is at 1: 1-1: 2, the aspect ratio is 1: 3, erecting a semi-soft plastic fiber filler in the upper space of the reaction chamber, arranging a sludge discharge perforated pipe in the middle of the reactor, arranging a slag discharge pipe at the bottom of the reactor, and connecting a water outlet of the hydrolysis acidification unit with a water inlet of the anaerobic reactor;
the anaerobic reactor adopts a carbon steel anti-corrosion tower structure, and the volume load is 4-10 kgCOD/m3D, ascending flow rate: 0.9-1.1m/h, head loss: 0.76m, the pH value of the sewage entering the anaerobic reactor is between 6.5 and 8, the tower body is heated and insulated to control the water temperature to be 30 ℃, polyurethane filler is adopted, water is distributed by a perforated pipe, the diameter of a water distribution hole is phi 15mm, and the service area of each hole is 1 to 2m2The water outlet of the anaerobic reactor is connected with the water inlet of the high-load aerobic tank;
the combined filler is suspended in the high-load aerobic tank, the surface of the filler is full of a biological membrane, the filling rate is 70 percent, and the volume load of the filler is 0.5-3.0 kgBOD/m3D, filling material, wherein the dissolved oxygen in the tank is 3-6 mg/L, supplying air into water through an air blower and a microporous disc aerator, the air-water ratio is 40-100: 1, and the effluent of the high-load aerobic tank is precipitated through an inclined plateThe sludge and water in the pool are separated and then enter a P-MBR deep aerobic biochemical section;
the P-MBR deep aerobic biochemical section removes refractory organic matters in the wastewater through biological metabolism of activated sludge and adsorption of active fillers, wherein the microbial biomass is more than 10g/L, and the gas-water ratio is as follows: 20:1, membrane flux: 13-15L/m2H, the particle size of the active filler is 100um, and the pore size of the membrane is 0.04 um.
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