CN113149154A - Method for oxidizing pollutants in water by coupling electricity/ozone/permanganate - Google Patents
Method for oxidizing pollutants in water by coupling electricity/ozone/permanganate Download PDFInfo
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- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
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- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
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Abstract
The invention discloses a method for oxidizing pollutants in water by coupling electricity/ozone/permanganate, which specifically comprises the following steps: injecting organic wastewater to be treated into a reaction chamber containing a cathode/anode electrode system, adding electrolyte into the organic wastewater to enable the concentration of the electrolyte to be 0.02-0.1 mol/L, and simultaneously turning on a direct current stabilized power supply to control the current density to be 10-200 mA/cm2And then introducing ozone and permanganate into the organic wastewater, and treating for a certain time under the action of an electric field. The method realizes coupling combination of processes, excites the intermediate valence state manganese ions with strong oxidation characteristic and increases the number of hydroxyl free radicals, thereby improving the treatment effect on organic wastewater, and reducing electricityCan input ozone and permanganate consumption, has high removal efficiency, and is not simple process superposition. Compared with the similar process, the method has the advantages of higher degradation efficiency, low cost, great reduction of energy consumption, suitability for large-scale application in various water body treatments, and good application prospect.
Description
Technical Field
The invention relates to the technical field of water treatment, in particular to a method for oxidizing pollutants in water by coupling electricity/ozone/permanganate.
Background
With the continuous development of society, environmental problems are increasingly severe, and pollutants entering water are various and huge in quantity, so that the safety guarantee of water in natural environment is threatened. Various organic pollutants found in water have the characteristics of low content, wide distribution, great harm, difficult removal and the like. Researches at home and abroad in recent years show that the refractory organic pollutants in water have genetic toxicity and can cause cancers and teratogenicity. Water pollution control has become a major issue of social focus.
Ozone, as an efficient oxidant, is widely used in the field of water treatment, and is often used as a pretreatment or advanced treatment technology for drinking water treatment. The oxidation of ozone has direct oxidation and indirect oxidation, the direct oxidation of ozone has stronger selectivity, and the oxidation capability and the mineralization capability of saturated hydrocarbon, benzene and chlorinated organic matters in water are weaker. In addition, the low solubility of ozone in water and the limited mass transfer efficiency between gas and liquid phases lead to a low ozone utilization rate in the direct oxidation process. The indirect oxidation of ozone generates hydroxyl radical (. OH) through a series of catalytic ozone reactions, which has strong non-selective oxidation capability. The pollutant degradation efficiency and the ozone utilization efficiency can be effectively improved through indirect oxidation. In recent years, the electrochemical catalysis ozone technology is widely concerned due to the characteristics of cleanness, high efficiency and green, but the generation efficiency of hydroxyl free radicals is low. Potassium permanganate is used as an oxidant in the traditional water treatment process, and has the advantages of convenient storage and transportation, relatively low price, difficult generation of toxic disinfection byproducts and the like. In the water treatment process in China, potassium permanganate is mainly used for controlling the smell of water, reducing the chromaticity of the water, inhibiting the growth and the propagation of algae in surface water and the like. Although potassium permanganate has certain oxidizing capacity to eliminate trace organic pollutant, potassium permanganate alone can eliminate some refractory matters with complicated structureThe potassium permanganate is oxidized, but a good removal effect cannot be achieved. In recent years, methods for exciting potassium permanganate to generate manganese ions with intermediate valence states, such as Mn (III), Mn (V) and Mn (VI), to oxidize refractory organic pollutants in water have attracted extensive attention. And the final product thereof is MnO2But also can absorb part of pollutants in the water. However, under general conditions, potassium permanganate hardly generates intermediate-valence manganese ions with oxidation characteristics, so that the degradation effect of potassium permanganate on pollutants is poor.
In order to solve the problems, researchers also make a great deal of research in recent years, for example, an invention patent CN1557736A discloses an oxidation coagulation aiding method combining ozone and potassium permanganate, the synergistic oxidation and catalytic oxidation effects of ozone and potassium permanganate are reduced or the side effect caused by adding ozone only is avoided, the method can be used as a pre-oxidation technology to enhance the removal of micro pollutants in water, remove odor in water, enhance the removal of algae in water and improve the coagulation aiding effect, but the method has the defect of low degradation rate when used in an advanced oxidation technology to mineralize pollutants; the invention patent CN101503242A discloses a water treatment agent for removing pollution by strengthening potassium permanganate by using intermediate manganese ions, a complexing agent is added to form a coordination complex with the intermediate manganese ions generated by oxidizing organic matters by potassium permanganate, and an inducer is used to accelerate the generation of the intermediate manganese ions, so that the generation speed of the intermediate manganese ions is increased, the utilization rate of the intermediate manganese ions is increased, the capability of oxidizing and degrading organic pollutants by potassium permanganate is strengthened, but other metal ions are introduced to generate secondary pollution, and the degradation rate is less than 80%; the invention patent CN103086478A discloses a method for treating oily wastewater by ozone and electrochemical synergetic oxidation, which enables the ozone oxidation and the electrochemical oxidation to have synergistic effect and overcomes the defect of pure O3The oxidation capacity is low during oxidation, but the disadvantages of high energy consumption and large ozone adding amount exist. Thereby limiting the practical application of the above degradation techniques in water treatment.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for oxidizing pollutants in water by coupling electricity/ozone/permanganate, and solves the problems of secondary pollution, large oxidant adding amount, high energy consumption, low active species generation efficiency and the like in the existing advanced oxidation method for degrading organic pollutants.
In order to solve the technical problems, the invention adopts the following technical scheme: a method for oxidizing pollutants in water by coupling electricity/ozone/permanganate, comprising the following steps:
injecting organic wastewater to be treated into a reaction chamber containing a cathode/anode electrode system, adding electrolyte into the organic wastewater to enable the concentration of the electrolyte to be 0.02-0.1 mol/L, and simultaneously turning on a direct current stabilized power supply to control the current density to be 10-200 mA/cm2And then introducing ozone and permanganate into the organic wastewater to enable the concentration of the ozone to be 1-10 mg/L and the concentration of the permanganate to be 50-500 mu mol/L, and performing electric field treatment to complete treatment of organic pollutants in the organic wastewater.
Thus, under energized conditions, ozone can be directly reduced by the cathode to generate hydroxyl radicals (. OH). Under the action of an electric field, the permanganate can also obtain electrons through the cathode to generate intermediate-valence manganese ions (Mn (III), Mn (V) and Mn (VI)) with strong oxidizing property, and meanwhile, the ozone can also oxidize the low-valence manganese ions into high-valence manganese ions to further oxidize organic matters in the water. In addition, the permanganate and the manganese compound with the intermediate valence state also have the capability of synergistically catalyzing ozone to generate more hydroxyl radicals, so that the degradation efficiency of pollutants difficult to degrade can be further improved. It can be seen that a coupling oxidation system exists among the ozone oxidation method, the electrochemical catalysis method and the permanganate oxidation method, the treatment efficiency of the coupling oxidation system on organic matters is far higher than that of the cathode catalysis ozone oxidation method, the permanganate catalysis ozone method or the electrically enhanced permanganate synergistic oxidation method, and the coupling oxidation system is not the sum of simple superposition of the oxidation methods.
Preferably, the electric field treatment time is 20 to 60 min.
Preferably, the flow rate of the ozone is 60-500 ml/min. The ozone is added in an aeration mode, and the air source of the ozone generator can be an air source or an oxygen source.
Preferably, the permanganate is one or more of potassium permanganate and sodium permanganate.
Preferably, the electrolyte is one or more of a hydrochloride and a sulfate.
Preferably, the sulfate is selected from at least one of sodium sulfate and potassium sulfate; the hydrochloride is at least one selected from sodium chloride and potassium chloride.
The invention also aims to provide a special oxidation device adopting the method, which comprises a reaction chamber, a direct current power supply, a cathode, an anode and an aeration device, wherein the reaction chamber is provided with a water inlet, a water outlet and a chemical feeding port, the reaction chamber is internally provided with at least one overflow plate, the reaction chamber is divided into a plurality of stages by the overflow plate, the cathode is plated on the inner wall of the reaction chamber and the plate wall of the overflow plate in a plating manner, and the cathode of the direct current power supply is connected with the cathode through a lead; the anode is inserted into the reaction chamber from the top of each stage of reaction chamber, and the anode of the direct current power supply is connected with the anode through a lead; the aeration devices are uniformly distributed at the bottom of the reaction chamber in the form of aeration pipes.
Therefore, the cathode is plated on the inner wall of the reaction chamber and the plate wall of the overflow plate in a plating mode, so that the contact area between the treated sewage and the cathode electrode is increased, the activation rate of permanganate is increased, the usage amount of metal is reduced, and the cost is reduced.
Preferably, when a plurality of overflow plates are used, the plurality of overflow plates are positioned equidistantly.
Preferably, an insulating separator is arranged between the cathode and the anode.
Like this, can adjust the number of overflow plate according to the requirement of the quality of water of intaking and the quality of water of going out among the practical engineering application, it separates the reaction chamber for different reaction compartments to increase the overflow plate number, different reaction voltage can be selected to different reaction compartments, pending water is through first order reaction compartment processing back, get into next order reaction compartment further processing through the overflow plate overflow, thereby realize the deep level of pending water and handle, and sewage of different concentrations can be handled to every order reaction compartment, the concentration range of pollutant in pending aquatic has been widened, make permanganate can be aroused more efficiently, also make the electric energy obtain more reasonable utilization. When the number of the overflow plates is increased to a certain number, the distance between the cathode and the anode is closer, and an insulating separation plate needs to be added between the cathode and the anode.
Preferably, the anode and the cathode are each independently selected from a graphite electrode, a metal electrode or a metal composite electrode.
The graphite electrode is a graphite rod electrode, a graphite wire electrode, a graphite felt electrode, a graphite plate electrode, a graphite sponge electrode, a graphite particle electrode or a porous graphite electrode; the electrode in the metal composite electrode is a composite electrode modified by one or more of metal, metal oxide and metal hydroxide, and the metal is a metal element in the 4 th to 6 th periods of the periodic table, such as a titanium platinum-plated electrode or a nickel platinum-plated electrode.
Compared with the prior art, the invention has the following beneficial effects:
1. the method utilizes the electricity/ozone/permanganate coupling oxidation to directly reduce ozone at the cathode to generate hydroxyl radicals (OH), and simultaneously the permanganate obtains electrons at the cathode to generate intermediate valence state manganese ions (Mn (III), Mn (V) and Mn (VI)) with strong oxidizing property, thereby rapidly degrading organic pollutants. In addition, MnO is a product of reduction of permanganate2And Mn2+The catalyst can also catalyze ozone to generate more hydroxyl free radicals (. OH), realizes coupling combination among different technologies, promotes the generation of manganese ions with intermediate valence states, and increases the generation amount of the hydroxyl free radicals, thereby improving the treatment effect on the organic wastewater, having high removal efficiency and not being simple process superposition.
2. The special oxidation device provided by the invention divides the reaction chamber into different reaction compartments by the arrangement of the overflow plate, and different reaction compartments can select different reaction voltages, so that the concentration range of pollutants in water to be treated is widened, ozone and permanganate can be excited more efficiently, and electric energy can be utilized more reasonably. Further, the cathode is plated on the inner wall of the reaction chamber and the plate wall of the overflow plate to form a plating layer, so that the contact area of ozone, permanganate and the cathode is increased, the yield of hydroxyl radicals and intermediate valence state manganese ions is increased, the consumption of metal is reduced, and the cost is reduced. Moreover, ozone is added into the reactor in an aeration mode, and when strong oxidizing ozone oxidizes organic matters, bubbles play a role in increasing the turbulence of fluid, so that organic pollutants in water are in full contact reaction with hydroxyl radicals and intermediate valence state manganese ions, an additional mixing device is not needed, and the reaction efficiency is improved.
3. The method provided by the invention is simple, green and economical, can degrade organic matters only under the input of small energy, reduces the input of electric energy and the consumption of ozone and permanganate, has strong degradation capability on the organic matters in the wastewater, is suitable for being popularized and used in large-scale engineering, and has good application prospect.
Drawings
FIG. 1 is a schematic structural diagram of a special oxidation apparatus of the present invention.
FIG. 2 is a graph showing the time-removal rate of diclofenac in the wastewater in example 1.
FIG. 3 is a graph showing the time-removal rate of diclofenac in the wastewater in example 2.
FIG. 4 is a graph showing the time-removal rate of diclofenac in the wastewater of example 3.
FIG. 5 is a graph showing the time-removal rate of diclofenac in the wastewater of example 4.
FIG. 6 is a graph showing the time-removal rate of diclofenac in the wastewater of example 5.
FIG. 7 is a graph showing the time-removal rate of sulfamethoxazole in the wastewater of example 6.
FIG. 8 is a graph showing the time-removal rate of phenol from the waste water in example 7.
FIG. 9 is a graph showing the time-removal rate of diclofenac in wastewater in comparative example 1.
FIG. 10 is a graph showing the time-removal rate of diclofenac in wastewater in comparative example 2.
FIG. 11 is a graph showing the time-removal rate of diclofenac in wastewater in comparative example 3.
FIG. 12 is a graph showing the time-removal rate of diclofenac in wastewater in comparative example 4.
Detailed Description
The present invention will be described in further detail with reference to examples.
Referring to fig. 1, the oxidation apparatus used in the present invention comprises a reaction chamber 11, a dc power supply 7, a cathode 8 and two anodes 4, wherein a water inlet 1 is arranged on a sidewall of the bottom of the reaction chamber 11, a water outlet 2 is arranged on a sidewall of the top of the reaction chamber 11, an exhaust port 9, an electrolyte dosing pipe 3 and a permanganate dosing pipe 10 are arranged on the top of the reaction chamber 11, an overflow plate 12 is arranged in the reaction chamber 11 to divide the reaction chamber 11 into two stages of reaction chambers, each stage of reaction chamber is separated by the overflow plate 12, the cathode 8 is plated on an inner wall of the reaction chamber 11 and a plate wall of the overflow plate 12 in a plating manner, the two anodes 4 are respectively inserted into the reaction chamber from the top of each stage of reaction chamber, the cathode 8 is connected with a negative electrode of the dc power supply 7 through a lead 6, the anode 4 is connected with a positive electrode of the dc power supply 7 through a lead 6, an observation port 5 is arranged on the top of the reaction chamber 11 for observing the internal conditions of the reaction chamber 11, an aeration pipe 13 is arranged at the bottom of the reaction chamber 11, and an aeration head 14 is arranged on the aeration pipe 13 and used for introducing gaseous ozone into the reactor 11.
During the concrete implementation, can be according to the requirement adjustment overflow plate's of the quality of water of intaking and the quality of water of going out the water number, it separates the reaction chamber for different reaction compartments to increase the overflow plate number, different reaction voltage can be selected in different reaction compartments, pending water is through first order reaction compartment processing back, get into next stage reaction compartment further processing through the overflow plate overflow, thereby realize the deep level of pending water and handle, and sewage of different concentrations can be handled to every stage reaction compartment, the concentration range of the aquatic pollutant of pending is widened, make permanganate can be aroused more efficiently, also make the electric energy obtain more reasonable utilization. When the number of the overflow plates is increased to a certain number, the distance between the cathode and the anode is closer, and an insulating separation plate needs to be added between the cathode and the anode. Wherein, the plurality of overflow plates are arranged equidistantly.
Example 1
The electrode reactor of the oxidation device is adopted to treat the sewage containing diclofenac of 60 mu mol/L, and the method specifically comprises the following steps:
injecting the sewage to be treated into a reaction chamber of a cathode/anode electrode system (an anode is a titanium platinum electrode, and a cathode is the titanium platinum electrode), adding sodium sulfate to ensure that the concentration of the sodium sulfate is 0.05 mol/L, adding a potassium permanganate aqueous solution to ensure that the concentration of the potassium permanganate is 100 mu mol/L, adding ozone at an aeration speed of 60 ml/min to ensure that the concentration of the ozone is 1 mg/L, starting a direct current power supply, keeping the concentration of the permanganate at 100 mu mol/L and the external current intensity at 20 mA, and discharging the treated sewage from a water outlet after treating for 20 min.
The change of the concentration of diclofenac in the wastewater to be treated in this example was recorded, the removal rate was calculated, and a time-removal rate graph of diclofenac was plotted, as shown in fig. 2. As can be seen from FIG. 2, in this example, the removal rate of diclofenac after 20min is 87.08%.
Example 2
The electrode reactor of the oxidation device is adopted to treat the sewage containing diclofenac of 60 mu mol/L, and the method specifically comprises the following steps:
injecting the sewage to be treated into a reaction chamber of a cathode/anode electrode system (an anode is a titanium platinum electrode, and a cathode is the titanium platinum electrode), adding sodium sulfate to ensure that the concentration of the sodium sulfate is 0.05 mol/L, adding a potassium permanganate aqueous solution to ensure that the concentration of the potassium permanganate is 150 mu mol/L, adding ozone at an aeration speed of 60 ml/min to ensure that the concentration of the ozone is 1 mg/L, starting a direct current power supply, keeping the concentration of the permanganate at 150 mu mol/L and the external current intensity at 20 mA, and discharging the treated sewage from a water outlet after treating for 20 min.
The change of the concentration of diclofenac in the wastewater to be treated in this example was recorded, the removal rate was calculated, and a time-removal rate graph of diclofenac was plotted, as shown in fig. 3. As can be seen from FIG. 3, in this example, the removal rate of diclofenac after 20min is 90.81%.
Example 3
The electrode reactor of the oxidation device is adopted to treat the sewage containing diclofenac of 60 mu mol/L, and the method specifically comprises the following steps:
injecting the sewage to be treated into a reaction chamber of a cathode/anode electrode system (an anode is a titanium platinum electrode, and a cathode is the titanium platinum electrode), adding sodium sulfate to ensure that the concentration of the sodium sulfate is 0.05 mol/L, adding a potassium permanganate aqueous solution to ensure that the concentration of the potassium permanganate is 100 mu mol/L, adding ozone at an aeration speed of 60 ml/min to ensure that the concentration of the ozone is 2.5 mg/L, starting a direct current power supply, keeping the concentration of the permanganate at 100 mu mol/L and the external current intensity at 20 mA, and discharging the treated sewage from a water outlet after 20min treatment.
The change of the concentration of diclofenac in the wastewater to be treated in this example was recorded, the removal rate was calculated, and a time-removal rate graph of diclofenac was plotted, as shown in fig. 4. As can be seen from FIG. 4, in this example, the diclofenac removal rate after 20min reached 91.91%.
Example 4
The electrode reactor of the oxidation device is adopted to treat the sewage containing diclofenac of 60 mu mol/L, and the method specifically comprises the following steps:
injecting the sewage to be treated into a reaction chamber of a cathode/anode electrode system (an anode is a titanium platinum electrode, and a cathode is the titanium platinum electrode), adding sodium sulfate to ensure that the concentration of the sodium sulfate is 0.05 mol/L, adding a potassium permanganate aqueous solution to ensure that the concentration of the potassium permanganate is 100 mu mol/L, adding ozone at an aeration speed of 60 ml/min to ensure that the concentration of the ozone is 1 mg/L, starting a direct current power supply, keeping the concentration of the permanganate at 100 mu mol/L and the external current intensity at 100 mA, and discharging the treated sewage from a water outlet after 20min treatment.
The change of the concentration of diclofenac in the wastewater to be treated in this example was recorded, the removal rate was calculated, and a time-removal rate graph of diclofenac was plotted, as shown in fig. 5. As can be seen from FIG. 5, in this example, the removal rate of diclofenac after 20min is 91.93%.
Example 5
The electrode reactor of the oxidation device is adopted to treat the sewage containing diclofenac of 20 mu mol/L, and the method specifically comprises the following steps:
injecting the sewage to be treated into a cathode/anode electrode system (the anode is a titanium platinum-plated electrode, and the cathode is the titanium platinum-plated electrode) reaction chamber, adding sodium sulfate to ensure that the concentration of the sodium sulfate is 0.05 mol/L, and adding potassium permanganate to dissolve the sodium sulfate in waterThe concentration of potassium permanganate is 100 mu mol/L, and the flow rate is 60 ml.min-1Ozone is added at the aeration speed to ensure that the concentration of the ozone is 1 mg/L, a direct current power supply is started, the concentration of permanganate is kept at 100 mu mol/L and the intensity of impressed current is kept at 20 mA, and after 20min of treatment, the treated sewage is discharged from a water outlet.
The change of the concentration of diclofenac in the wastewater to be treated in this example was recorded, the removal rate was calculated, and a time-removal rate graph of diclofenac was plotted, as shown in fig. 6. As can be seen from FIG. 6, in this example, the diclofenac removal rate after 20min was 99.43%.
Example 6
The method for treating the sewage containing the sulfamethoxazole by adopting the electrode reactor of the oxidation device comprises the following steps:
injecting the sewage to be treated into a reaction chamber of a cathode/anode electrode system (the anode is a titanium platinum-plated electrode, and the cathode is the titanium platinum-plated electrode), adding sodium sulfate to ensure that the concentration of the sodium sulfate is 0.05 mol/L, adding a potassium permanganate aqueous solution to ensure that the concentration of the potassium permanganate is 100 mu mol/L, and controlling the flow rate to be 60 ml/min-1Ozone is added at the aeration speed to ensure that the concentration of the ozone is 1 mg/L, a direct current power supply is started, the concentration of permanganate is kept at 100 mu mol/L and the intensity of impressed current is kept at 20 mA, and after 20min of treatment, the treated sewage is discharged from a water outlet.
The concentration change of sulfamethoxazole in the sewage to be treated in this example was recorded, the removal rate was calculated, and a time-removal rate graph of sulfamethoxazole was plotted, as shown in fig. 7. As can be seen from fig. 7, in this example, the removal rate of sulfamethoxazole after 20min reached 84.23%.
Example 7
The method for treating the sewage containing 60 mu mol/L phenol by adopting the electrode reactor of the oxidation device comprises the following steps:
injecting the sewage to be treated into a reaction chamber of a cathode/anode electrode system (the anode is a titanium platinum-plated electrode, and the cathode is the titanium platinum-plated electrode), adding sodium sulfate to ensure that the concentration of the sodium sulfate is 0.05 mol/L, adding a potassium permanganate aqueous solution to ensure that the concentration of the potassium permanganate is 100 mu mol/L, and controlling the flow rate to be 60 ml/min-1Ozone is added at the aeration speed to ensure that the concentration of the ozone is 1 mg/L,starting a direct current power supply and keeping the concentration of permanganate at 100 mu mol-1And the external current intensity is 20 mA, and after 20min of treatment, the treated sewage is discharged from a water outlet.
The change of the concentration of phenol in the wastewater to be treated in this example was recorded, and the removal rate was calculated, and a graph of time-removal rate of phenol was plotted, as shown in FIG. 8. As can be seen from FIG. 8, in this example, the removal rate of phenol reached 100% after 20 min.
Comparative example 1
The method for treating the sewage containing the diclofenac of 60 mu mol/L by adopting the electrode reactor of the oxidation device comprises the following steps:
injecting the sewage to be treated into a cathode/anode electrode system (the anode is a titanium platinum-plated electrode, the cathode is a titanium platinum-plated electrode), adding sodium sulfate into a reaction chamber to enable the concentration of the sodium sulfate to be 0.05 mol/L, adding a potassium permanganate aqueous solution to enable the concentration of the potassium permanganate to be 100 mu mol/L, adding ozone at an aeration speed of 60 ml/min to enable the concentration of the ozone to be 1 mg/L, not switching on a direct-current power supply, keeping the concentration of the permanganate to be 100 mu mol/L, and discharging the treated sewage from a water outlet after treating for 20 min.
The change of the concentration of diclofenac in the wastewater to be treated in this example was recorded, the removal rate was calculated, and a time-removal rate graph of diclofenac was plotted, as shown in fig. 9. As can be seen from FIG. 9, in this example, the diclofenac removal rate after 20min reached 67.04%.
Comparative example 2
The electrode reactor of the oxidation device is adopted to treat the sewage containing diclofenac of 60 mu mol/L, and the method specifically comprises the following steps:
injecting the sewage to be treated into a cathode/anode electrode system (the anode is a titanium platinum-plated electrode, the cathode is a titanium platinum-plated electrode), adding sodium sulfate into a reaction chamber to enable the concentration of the sodium sulfate to be 0.05 mol/L, adding a potassium permanganate aqueous solution to enable the concentration of the potassium permanganate to be 100 mu mol/L, starting a direct current power supply, keeping the concentration of permanganate to be 100 mu mol/L and the external current intensity to be 20 mA, and discharging the treated sewage from a water outlet after 20min treatment.
The change of the concentration of diclofenac in the wastewater to be treated in this example was recorded, the removal rate was calculated, and a time-removal rate graph of diclofenac was plotted, as shown in fig. 10. As can be seen from FIG. 10, in this example, the diclofenac removal rate after 20min was 70.38%.
Comparative example 3
The electrode reactor of the oxidation device is adopted to treat the sewage containing diclofenac of 60 mu mol/L, and the method specifically comprises the following steps:
injecting the sewage to be treated into a cathode/anode electrode system (the anode is a titanium platinum electrode, and the cathode is a titanium platinum electrode), adding sodium sulfate into a reaction chamber to ensure that the concentration of the sodium sulfate is 0.05 mol/L, adding ozone into the reaction chamber at an aeration speed of 60 ml/min to ensure that the concentration of the ozone is 1 mg/L, starting a direct current power supply, keeping the intensity of the applied current at 20 mA, and discharging the treated sewage from a water outlet after 20min of treatment.
The change of the concentration of diclofenac in the wastewater to be treated in this example was recorded, the removal rate was calculated, and a time-removal rate graph of diclofenac was plotted, as shown in fig. 11. As can be seen from FIG. 11, in this example, the diclofenac removal rate after 20min reached 21.23%.
Compared with the organic pollution treated by the electrochemical cathode catalytic ozonation, the removal rate of the diclofenac is improved by 65.85% under the same conditions as in the comparative example 1 and the comparative examples 1 to 3; compared with organic pollution treatment by ozone catalyzed by permanganate, the removal rate of diclofenac is improved by 20.04 percent; compared with the organic pollution treatment by electrically enhanced permanganate, the removal rate of the diclofenac is improved by 16.7 percent. Therefore, the effect of the invention is obviously better than that of other treatment modes, and is not simple superposition of the effects of the two treatment modes, and the generation efficiency of the manganese ions with the middle valence state and the hydroxyl radicals is greatly enhanced because the coupling effect exists among the electricity, the ozone and the permanganate.
Comparative example 4
The conventional cathode/anode reactor (not the oxidation device of the invention) is adopted to treat the wastewater containing 60 mu mol/L of diclofenac, and the method specifically comprises the following steps:
injecting the sewage to be treated into a reaction chamber of a cathode/anode electrode system (an anode is a titanium platinum electrode, and a cathode is the titanium platinum electrode), adding sodium sulfate to ensure that the concentration of the sodium sulfate is 0.05 mol/L, adding a potassium permanganate aqueous solution to ensure that the concentration of the potassium permanganate is 100 mu mol/L, adding ozone at an aeration speed of 60 ml/min to ensure that the concentration of the ozone is 1 mg/L, starting a direct current power supply, keeping the concentration of the permanganate at 100 mu mol/L and the external current intensity at 20 mA, and discharging the treated sewage from a water outlet after treating for 20 min.
The change of the concentration of diclofenac in the wastewater to be treated in this example was recorded, the removal rate was calculated, and a time-removal rate graph of diclofenac was plotted, as shown in fig. 12. As can be seen from FIG. 12, in this example, the diclofenac removal rate after 20min reached 9.03%.
Comparing example 1 with comparative example 4, it can be seen that the use of the special oxidation apparatus of the present invention can significantly improve the diclofenac removal rate by electricity/ozone/permanganate, which is probably because the cathode is plated on the inner wall of the reaction chamber and the wall of the overflow plate, which increases the contact area between the treated sewage and the cathode electrode, thereby accelerating the activation rate of permanganate and the efficiency of generating hydroxyl radicals. And the arrangement of the overflow plate in the reaction chamber realizes the deep treatment of the water to be treated, so that the permanganate can be more efficiently excited.
The above description is only exemplary of the present invention and should not be taken as limiting, and any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for oxidizing pollutants in water by coupling electricity/ozone/permanganate, which is characterized by comprising the following steps:
injecting organic wastewater to be treated into a reaction chamber containing a cathode/anode electrode system, adding electrolyte into the organic wastewater to enable the concentration of the electrolyte to be 0.02-0.1 mol/L, and simultaneously turning on a direct current stabilized power supply to control the current density to be 10-200 mA/cm2Then, introducing ozone and permanganate into the organic wastewater, and carrying out electric field treatment under the conditions that the concentration of the ozone is 1-10 mg/L and the concentration of the permanganate is 50-500 mu mol/L, namely finishing the treatment of the organic wastewaterAnd (4) treating organic pollutants.
2. The method for the electric/ozone/permanganate coupling oxidation of pollutants in water according to claim 1, wherein the electric field treatment time is 20-60 min.
3. The method for the electric/ozone/permanganate coupling oxidation of pollutants in water according to claim 1, wherein the flow rate of the introduced ozone is 60-500 ml/min.
4. The method of electrically/ozonately/permanganate coupling oxidation of pollutants in water according to claim 1, wherein the permanganate is one or more of potassium permanganate and sodium permanganate.
5. The method of claim 1, wherein the electrolyte is one or more of a hydrochloride and a sulfate.
6. The method for the coupled oxidation of pollutants in water with electricity/ozone/permanganate according to claim 5, wherein the sulfate is selected from at least one of sodium sulfate and potassium sulfate; the hydrochloride is at least one selected from sodium chloride and potassium chloride.
7. A special oxidation device adopting the method as claimed in any one of claims 1 to 6, comprising a reaction chamber, a DC power supply, a cathode, an anode and an aeration device, wherein the reaction chamber is provided with a water inlet, a water outlet and a chemical feeding port, the reaction chamber is internally provided with at least one overflow plate, the overflow plate divides the reaction chamber into a plurality of stages of reaction chambers, the cathode is plated on the inner wall of the reaction chamber and the plate wall of the overflow plate in a plating manner, and the cathode of the DC power supply is connected with the cathode through a lead; the anode is inserted into the reaction chamber from the top of each stage of reaction chamber, and the anode of the direct current power supply is connected with the anode through a lead; the aeration devices are uniformly distributed at the bottom of the reaction chamber in the form of aeration pipes.
8. The dedicated oxidizing device according to claim 7, wherein the plurality of overflow plates are disposed at equal distances from each other.
9. The dedicated oxidizing device according to claim 7, wherein an insulating separator is disposed between the cathode and the anode.
10. The dedicated oxidizing device according to claim 7, wherein the anode and the cathode are each independently selected from a graphite electrode, a metal electrode, or a metal composite electrode.
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| CN115536183A (en) * | 2022-10-30 | 2022-12-30 | 南京理工大学 | Based on DSA (MnO) X -Ti) cathode ozone/electrochemical coupling printing and dyeing wastewater treatment method of water treatment system |
| CN116040785A (en) * | 2023-03-01 | 2023-05-02 | 中国石油化工股份有限公司 | Device and method for treating sulfur-containing organic wastewater |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115536183A (en) * | 2022-10-30 | 2022-12-30 | 南京理工大学 | Based on DSA (MnO) X -Ti) cathode ozone/electrochemical coupling printing and dyeing wastewater treatment method of water treatment system |
| CN116040785A (en) * | 2023-03-01 | 2023-05-02 | 中国石油化工股份有限公司 | Device and method for treating sulfur-containing organic wastewater |
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