CN114212862A - Electric flocculation oxidation integrated wastewater treatment device and treatment method - Google Patents
Electric flocculation oxidation integrated wastewater treatment device and treatment method Download PDFInfo
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- CN114212862A CN114212862A CN202111152021.1A CN202111152021A CN114212862A CN 114212862 A CN114212862 A CN 114212862A CN 202111152021 A CN202111152021 A CN 202111152021A CN 114212862 A CN114212862 A CN 114212862A
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- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 25
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/463—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrocoagulation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The application discloses an electric flocculation oxidation integrated wastewater treatment device and a treatment method, and relates to the technical field of wastewater treatment. The device comprises a reactor, a power supply, an electric oxidation anode plate, an indirect electric flocculation cathode plate and a stirrer, wherein the reactor is used for containing wastewater, the electric oxidation anode plate and the indirect electric flocculation cathode plate are arranged in parallel, and at least one part of the electric oxidation anode plate and at least one part of the indirect electric flocculation cathode plate are both positioned in the reactor; the power supply is communicated with the electric oxidation anode plate and the indirect electric flocculation cathode plate through leads; the stirrer is used for controlling the mass transfer process of the wastewater in the reactor. The method is used for removing suspended pollutants and refractory organic pollutants in the wastewater.
Description
Technical Field
The application relates to the technical field of wastewater treatment, in particular to an electric flocculation oxidation integrated wastewater treatment device and a treatment method.
Background
The antibiotic wastewater has complex components, and generally has the characteristics of high suspended matter concentration, high organic matter concentration, low biodegradability and the like. In recent years, the treatment techniques for antibiotic wastewater mainly include physical methods (adsorption, air-float, coagulation, membrane filtration, etc.), biological methods (aerobic, anaerobic, microalgae, etc.), and advanced oxidation methods (ozone oxidation, Fenton oxidation, photocatalytic oxidation, etc.). The electrochemical technology is used as a clean water treatment process and has the characteristics of a physical method and an advanced oxidation method. According to different application modes of the electrode, multiple functions of air floatation, flocculation, oxidation, reduction, sterilization and the like can be realized, so that the electrode is often used for treating antibiotic wastewater.
In order to realize efficient treatment of antibiotic wastewater, patent CN 112811676 a discloses a method for degrading antibiotic-containing wastewater by using geopolymer particle three-dimensional electrodes, wherein geopolymer particles are prepared by using solid wastes such as steel slag and the like as the three-dimensional electrodes, and graphite is used as an anode and a cathode, so that a three-dimensional electrochemical system formed by the geopolymer particles can effectively degrade sulfamethoxazole in the antibiotic wastewater. The method improves the space utilization rate of an electrochemical system, but the preparation cost of the particle electrode is high, and the method has higher requirements on water quality conditions. Patent CN 113023842A discloses an electrochemical reinforced catalysis persulfate method for treating antibiotic wastewater, which couples two advanced oxidation processes of electrocatalytic oxidation and persulfate, takes DSA and stainless steel mesh as an anode and a cathode respectively, and CoFe2O4the/NF was used as a heterogeneous catalyst. Compared with the similar electrochemical water treatment technology, the method has higher levofloxacin degradation rate, but the catalyst has poorer recycling performance, and the effluent quality is difficult to keep stable. Patent CN 104085963A disclosureThe method couples two advanced oxidation processes of electrocatalytic oxidation and ozone catalytic oxidation, constructs the electrochemical combined ozone treatment device, and realizes the quick removal of amoxicillin in a short time. The method effectively improves the mineralization degree of antibiotics, but the equipment cost and the operation cost of the coupling process are higher and the function is single. The patent CN 110498491B discloses a treatment process for degrading antibiotic wastewater by a membrane filtration coupling system, the method couples two processes of electrocatalytic oxidation and membrane filtration, and the antibiotic wastewater can sequentially pass through the processes of negative electrode material titanium mesh, positive electrode material conductive film filtration, electrocatalytic degradation and the like to achieve the purpose of water purification. The method has the double functions of filtration and degradation, but the reactor has a complex structure and needs to be repeatedly cleaned.
Although the existing electrochemical technology can achieve efficient removal of antibiotics in antibiotic wastewater, the existing electrochemical technology is difficult to achieve synchronous and rapid removal of other types of pollutants. In the coupling process, wastewater generally passes through an electrochemical reactor and other water treatment process reactors in turn, and although pollutants can be effectively removed, the problems of high energy consumption of an electrochemical system, large occupied area and high construction and maintenance costs caused by coupling of multiple reactors still exist.
Disclosure of Invention
The application provides an electricity flocculation oxidation integration effluent treatment plant and processing method, and the device assembles the electricity oxidation positive pole and indirect electricity flocculation negative pole in same electrochemical reaction for the system has the dual function of oxidation and flocculation concurrently, realizes getting rid of jointly of the suspended pollutant in the short time aquatic and the organic pollutant of difficult degradation.
In order to achieve the purpose, the application provides an electric flocculation oxidation integrated wastewater treatment device which comprises a reactor, a power supply, an electric oxidation anode plate, an indirect electric flocculation cathode plate and a stirrer, wherein the reactor is used for containing wastewater, the electric oxidation anode plate and the indirect electric flocculation cathode plate are arranged in parallel, and at least one part of the electric oxidation anode plate and at least one part of the indirect electric flocculation cathode plate are both positioned in the reactor; the power supply is communicated with the electric oxidation anode plate and the indirect electric flocculation cathode plate through leads; the stirrer is used for controlling the mass transfer process of the wastewater in the reactor.
Further, the material of the electro-oxidation anode plate is one of BDD, ruthenium dioxide, titanium dioxide, tin dioxide and a titanium ruthenium-coated electrode; the indirect electric flocculation cathode plate is made of one of aluminum, magnesium and zinc.
Furthermore, the electrooxidation anode plate and the indirect electroflocculation cathode plate are both arranged in the reactor through clamping grooves, and the interval between the two clamping grooves is 0.5-1.5 cm.
Furthermore, the upper part of the side wall of the reactor is provided with a water inlet, the bottom of the side wall of the reactor, which is far away from the water inlet, is provided with a water outlet and a sludge discharge port, and the sludge discharge port is positioned below the water outlet.
Further, the stirrer is a magnetic stirrer or a paddle stirrer.
Furthermore, the magnetic stirrer is positioned below the reactor, and a magneton matched with the magnetic stirrer is arranged in the reactor.
Further, the power supply is a constant-current stabilized power supply or a pulse power supply.
The application also provides a wastewater treatment method which is realized based on the electric flocculation oxidation integrated wastewater treatment device and comprises the following steps:
step 1: injecting the wastewater into a reactor;
step 2: starting a power supply, and carrying out electrolysis treatment on the wastewater contained in the reactor, wherein the voltage of the power supply is less than 30V, and the electrolysis time is 10-60 min; simultaneously starting the stirrer, wherein the stirring speed is less than 500 rpm;
and step 3: and after the electrolysis is finished, the power supply and the stirrer are turned off, and treated effluent and generated flocculated sludge are separately discharged after sedimentation is carried out for 20-40 min.
Further, in the electrolysis process: the power voltage is 10V, the electrolysis time is 60min, the stirring speed is 300rpm, and the settling time is 30 min.
Compared with the prior art, the application has the following beneficial effects:
(1) the application can be used for advanced treatment of wastewater such as antibiotics, pesticides and dyes.
(2) The device is simple to assemble, low in energy consumption and capable of efficiently removing various pollutants and saving the operation cost. The current is smaller under the condition of constant voltage, and the energy consumption is lower.
(3) The anode and the cathode of the device act synchronously, the space utilization rate is higher, and the construction cost can be saved. The anode generates an electrooxidation reaction to further treat the organic pollutants, and the cathode generates an indirect electroflocculation reaction to further treat the macromolecular pollutants, so that more pollutants can be treated.
(4) The electrochemical system has the advantages that the requirements of the anode and the cathode on pH and conductivity are low, and the applicable water quality range is wider. Compared with the conventional electric flocculation, the indirect electric flocculation cathode has lower anode corrosion degree and longer service life of the metal plate.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present application, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic structural view of an integrated wastewater treatment device for electric flocculation and oxidation;
FIG. 2 is a schematic diagram of an operation mechanism of an integrated wastewater treatment device for electric flocculation and oxidation;
FIG. 3 is a graph comparing the turbidity and antibiotic removal performance of different cathode and anode plate combinations in example 3;
FIG. 4 is a graph showing the effect of turbidity and antibiotic removal simultaneously;
FIG. 5 is a graph showing the electrode surface changes of the anode and cathode of the aluminum plate at different electrolysis times.
In the figure, 1-an organic glass reactor, 2-a constant-current stabilized voltage power supply, 3-a magnetic stirrer, 4-a water inlet, 5-a water outlet, 6-a sludge discharge port, 7-an electro-oxidation anode plate, 8-an indirect electric flocculation cathode plate and 9-a magneton.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, 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 application.
In the description of the present application, it is to be understood that the terms "center", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", and the like indicate orientations or positional relationships based on those shown in the drawings, and are only for convenience in describing the present application and simplifying the description, but do not indicate or imply that the referred device or element must have a particular orientation, be constructed in a particular orientation, and be operated, and thus should not be construed as limiting the present application.
In the description of the present application, it is to be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; the specific meaning of the above terms in the present application can be understood in a specific case by those of ordinary skill in the art.
The terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present application, "a plurality" means two or more unless otherwise specified.
The application provides an electric flocculation oxidation integrated wastewater treatment device, which comprises a reactor, a power supply, an electric oxidation anode plate 7, an indirect electric flocculation cathode plate 8 and a stirrer, wherein the reactor is used for containing wastewater, the electric oxidation anode plate 7 and the indirect electric flocculation cathode plate 8 are arranged in parallel, and at least one part of the electric oxidation anode plate 7 and at least one part of the indirect electric flocculation cathode plate 8 are positioned in the reactor; the power supply is communicated with the electric oxidation anode plate 7 and the indirect electric flocculation cathode plate 8 through leads; the stirrer is used for controlling the mass transfer process of the wastewater in the reactor. This application assembles electro-oxidation positive pole 7 and indirect electric flocculation negative pole 8 in same electrochemical reaction for the system has the dual function of oxidation and flocculation concurrently, reaches the suspension pollutant in the short time aquatic and gets rid of jointly of difficult degradation organic pollutant.
As a preferred embodiment of the present invention, the material of the electrooxidation anode plate 7 is one of BDD, ruthenium dioxide, titanium dioxide, tin dioxide and titanium ruthenium-coated electrode, which exhibits excellent removal ability of organic substances as an anode. The indirect electric flocculation cathode plate 8 is made of one of aluminum, magnesium and zinc, and one of aluminum, magnesium and zinc is selected as a cathode, so that the long-time use of the electrode is facilitated.
As a preferred embodiment of the invention, the electric oxidation anode plate 7 and the indirect electric flocculation cathode plate 8 are both arranged in the reactor through clamping grooves, and the interval between the two clamping grooves is 0.5-1.5 cm.
As a preferred embodiment of the invention, the upper part of the side wall of the reactor is provided with a water inlet 4, the bottom of the side wall of the reactor far away from the water inlet is provided with a water outlet 5 and a sludge discharge port 6, and the sludge discharge port 6 is positioned below the water outlet 5. Valves are arranged at the water inlet 4, the water outlet 5 and the sludge discharge port 6.
As a preferred embodiment of the invention, the stirrer is a magnetic stirrer 3 or a paddle stirrer.
As a preferred embodiment of the invention, the magnetic stirrer 3 is positioned below the reactor, and the inside of the reactor is provided with the magnetons 9 matched with the magnetic stirrer 3, so that the mass transfer of the water body is more uniform.
In a preferred embodiment of the present invention, the power supply is a constant current stabilized power supply or a pulse power supply.
A wastewater treatment method is realized based on an electric flocculation oxidation integrated wastewater treatment device, and comprises the following steps:
step 1: injecting the wastewater into a reactor;
step 2: starting a power supply, and carrying out electrolysis treatment on the wastewater contained in the reactor, wherein the voltage of the power supply is less than 30V, and the electrolysis time is 10-60 min; simultaneously starting the stirrer, wherein the stirring speed is less than 500 rpm;
and step 3: and after the electrolysis is finished, the power supply and the stirrer are turned off, and treated effluent and generated flocculated sludge are separately discharged after sedimentation is carried out for 20-40 min.
As a preferred embodiment of the present invention, when the wastewater is electrolyzed under a power supply voltage of 10V, an electrolysis time of 60min, a stirring rate of 300rpm and a settling time of 30min, the turbidity and the chloramphenicol removal rate of the chloramphenicol mixed wastewater are 92.77% and 84.93%, respectively, and the turbidity and the sulfamethoxazole removal rate of the sulfamethoxazole mixed wastewater are 85.64% and 99.75%, respectively.
Example 1: referring to fig. 1, an electric flocculation oxidation integrated wastewater treatment device comprises an organic glass reactor 1, a constant-current stabilized voltage power supply 2, an electric oxidation anode plate 7, an indirect electric flocculation cathode plate 8, a magnetic stirrer 3 and a magneton 9.
The plexiglass reactor 1 has dimensions of 10cm by 8cm by 5cm and an effective volume of 400 mL. The upper part of the side wall of the sludge pump is provided with a water inlet 4, the bottom of the side wall of one side far away from the water inlet is provided with a water outlet 5 and a sludge discharge port 6, and the sludge discharge port 6 is positioned below the water outlet 5. The wastewater can enter the organic glass reactor 1 through the water inlet 4, after electrolytic treatment and sedimentation, the treated effluent flows out of the water outlet 5, and the generated flocculated sludge is discharged through the sludge discharge port 6. The top cover of the organic glass reactor 1 is provided with two clamping grooves for fixing the electric oxidation anode plate 7 and the indirect electric flocculation cathode plate 8. The interval between two draw-in grooves is 1 cm. Valves are arranged at the water inlet 4, the water outlet 5 and the sludge discharge port 6.
The electrooxidation anode plate 7 is a BDD anode with the size of 5cm multiplied by 6cm multiplied by 0.cm, and the indirect electroflocculation cathode plate 8 is an aluminum cathode with the size of 5cm multiplied by 6cm multiplied by 0.2 cm. The two polar plates are fixed inside the organic glass reactor 1 in parallel through the clamping grooves.
The constant-current stabilized voltage power supply 2 is positioned above the organic glass reactor 1, can be communicated with the electric oxidation anode plate 7 and the indirect electric flocculation cathode plate 8 through a conducting wire, supplies energy to the electric oxidation anode plate 7 and the indirect electric flocculation cathode plate 8 by using the constant-current stabilized voltage power supply 2 in the treatment process, and controls the voltage range of a system to be 0-30V by adopting a constant-voltage mode.
The magnetic stirrer 3 is positioned below the organic glass reactor 1, the magnetons 9 matched with the magnetic stirrer 3 are positioned in the organic glass reactor 1, and the magnetic stirrer 3 and the magnetons 9 are used for controlling the mass transfer process of the water body in the treatment process.
Referring to fig. 2, the working principle of the device of the present embodiment is as follows: under the action of sufficient voltage, oxygen is generated at the anode, hydrogen is generated at the cathode, and meanwhile, a large amount of hydroxide ions are generated near the cathode, and the hydroxide ions attack the aluminum cathode, so that aluminum ions are separated out, and an aluminum coagulant with a flocculation effect is further generated.
The progress of the anodic oxidation reaction is shown in equations (1) and (2):
BDD+H2O→BDD(·OH)+H++e- (1)
organic +. OH → product (2)
The process of the cathode indirect flocculation reaction is shown in formulas (3) and (4):
example 2: in this example, turbidity and chloramphenicol, turbidity and sulfamethoxazole were removed simultaneously by using the wastewater treatment apparatus integrated with electric flocculation and oxidation in example 1. The method comprises the following steps:
step 1: the mixed wastewater enters the organic glass reactor through the water inlet under the action of the water inlet pump;
step 2: when water enters, a constant-current voltage-stabilized power supply 2 is connected, a magnetic stirrer 3 is started, the voltage is controlled to be 10V for electrolysis, the electrolysis time is 60min, and the stirring speed is controlled to be 300rpm, so that the mass transfer is uniform;
and step 3: precipitating for 30min after the electrolysis treatment is finished, then opening a valve of a water outlet 5, and discharging treated effluent in the organic glass reactor 1 from the water outlet 5; and opening a valve of the sludge discharge port 6, and discharging the flocculated sludge generated in the organic glass reactor 1 through the sludge discharge port 6.
The treatment effect is shown in fig. 4, the turbidity removal rate of the turbidity and the chloramphenicol mixed wastewater after the advanced treatment is 92.77%, and the chloramphenicol removal rate is 84.93%; the turbidity after the advanced treatment and the turbidity removal rate of the sulfamethoxazole mixed wastewater are 85.64 percent and the sulfamethoxazole removal rate is 99.75 percent.
Example 3: the removal effect of the four electrode combination systems on turbidity, chloramphenicol and sulfamethoxazole was examined using the apparatus as shown in fig. 1 and the method in example 2.
The sizes of the electrode plates are 5cm multiplied by 6cm multiplied by 0.2cm, the anode plates can be set to be BDD, aluminum plates and stainless steel nets, the cathode plates can be set to be aluminum plates and stainless steel nets to assemble four systems of BDD-Al, BDD-SS, SS-Al and Al-SS, and the two electrode plates are parallelly fixed in the reactor at the interval of 1cm through a clamping groove. Controlling the voltage to be 10V for electrolysis, controlling the electrolysis time to be 60min, and controlling the stirring speed to be 300 rpm. Treatment effect as shown in fig. 3, BDD showed excellent removal ability for organic matter as an anode; when the aluminum is used as the cathode, the effect of removing turbidity is obvious, and the effect of removing organic matters is also certain.
Example 4: the degree of corrosion of the aluminum electrode was examined using the apparatus shown in FIG. 1. Controlling the voltage to be 5V for electrolysis, wherein the electrolysis time is 0min, 20min, 40min and 60min, and observing the surface change of the electrode at different times when the aluminum is respectively used as an anode and a cathode by a scanning electron microscope. As shown in fig. 5, the upper part is the degree of surface corrosion of the aluminum plate as the anode, and the lower part is the degree of surface corrosion of the aluminum plate as the cathode, and it can be found that the degree of surface corrosion of the electrode is weaker when aluminum is used as the cathode than when aluminum is used as the anode, which is more advantageous for the long-term use of the electrode.
The above is only an embodiment of the present application, but the scope of the present application is not limited thereto, and any changes or substitutions within the technical scope of the present disclosure should be covered by the scope of the present application. Therefore, the protection scope of the present application shall be subject to the protection scope of the claims.
Claims (9)
1. An electric flocculation oxidation integrated wastewater treatment device is characterized by comprising a reactor, a power supply, an electric oxidation anode plate, an indirect electric flocculation cathode plate and a stirrer, wherein the reactor is used for containing wastewater; the power supply is communicated with the electric oxidation anode plate and the indirect electric flocculation cathode plate through leads; the stirrer is used for controlling the mass transfer process of the wastewater in the reactor.
2. The integrated wastewater treatment device for electric flocculation and oxidation as claimed in claim 1, wherein the material of the electric oxidation anode plate is one of BDD, ruthenium dioxide, titanium dioxide, tin dioxide and titanium ruthenium-coated electrode; the indirect electric flocculation cathode plate is made of one of aluminum, magnesium and zinc.
3. The integrated wastewater treatment device of claim 1, wherein the electro-oxidation anode plate and the indirect electro-flocculation cathode plate are both arranged inside the reactor through clamping grooves, and the interval between the two clamping grooves is 0.5-1.5 cm.
4. The integrated wastewater treatment device for electric flocculation oxidation according to any one of claims 1 to 3, wherein the upper part of the side wall of the reactor is provided with a water inlet, the bottom of the side wall of the reactor far away from the water inlet is provided with a water outlet and a sludge discharge port, and the sludge discharge port is positioned below the water outlet.
5. The integrated wastewater treatment device for electric flocculation and oxidation as claimed in claim 1, wherein the stirrer is a magnetic stirrer or a paddle stirrer.
6. The integrated wastewater treatment device for electric flocculation and oxidation as claimed in claim 5, wherein the magnetic stirrer is located below the reactor, and a magneton matched with the magnetic stirrer is arranged in the reactor.
7. The integrated wastewater treatment device for electric flocculation and oxidation as claimed in claim 1, wherein the power supply is a constant current stabilized power supply or a pulse power supply.
8. A wastewater treatment method is realized based on the electric flocculation oxidation integrated wastewater treatment device of any one of claims 1 to 7, and comprises the following steps:
step 1: injecting the wastewater into a reactor;
step 2: starting a power supply, and carrying out electrolysis treatment on the wastewater contained in the reactor, wherein the voltage of the power supply is less than 30V, and the electrolysis time is 10-60 min; simultaneously starting the stirrer, wherein the stirring speed is less than 500 rpm;
and step 3: and after the electrolysis is finished, the power supply and the stirrer are turned off, and treated effluent and generated flocculated sludge are separately discharged after sedimentation is carried out for 20-40 min.
9. A method for treating wastewater according to claim 8, wherein, in the electrolysis process: the power voltage is 10V, the electrolysis time is 60min, the stirring speed is 300rpm, and the settling time is 30 min.
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