CN108928890B - Method for treating refractory wastewater by three-dimensional electrode coupling oxidant - Google Patents
Method for treating refractory wastewater by three-dimensional electrode coupling oxidant Download PDFInfo
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Abstract
The invention belongs to the field of treatment of refractory wastewater, and provides a method for treating refractory wastewater by using a three-dimensional electrode coupled oxidant, which comprises the following steps: adding refractory wastewater to be treated with the pH value of 3-11 into a wastewater treatment container with a plate-type anode and a plate-type cathode, adding an oxidant and a particle electrode into the wastewater treatment container, stirring to enable the particle electrode to be in a fluidized state, starting a direct current power supply connected with the plate-type anode and the plate-type cathode, and controlling the current density to be 2-20 mA/cm2Treating for 15-60 min under the condition of (1), and finishing the treatment of the refractory wastewater; the particle electrode is a magnetic spinel ferrite MFe2O4The oxidant is at least one of persulfate, hydrogen peroxide and ozone. The method provided by the invention can effectively improve the degradation efficiency and the degradation effect of the refractory wastewater while reducing the wastewater treatment cost.
Description
Technical Field
The invention belongs to the field of treatment of refractory wastewater, and relates to a method for treating refractory wastewater by using a three-dimensional electrode coupled oxidant.
Background
Some of the waste water discharged from industrial processes often contains a large amount of harmful and very difficult to degrade organic pollutants. Moreover, water pollution caused by some novel pollutants such as herbicide pesticides, antibiotic drugs and the like is also an important environmental problem. Traditional biological treatment, heat treatment, adsorption, physical and chemical treatment methods and membrane treatment methods have been applied to the removal of these refractory organic pollutants, however, in practical application, some technical defects, such as long reaction time, unobvious treatment effect of the refractory pollutants, serious secondary pollution, etc., are exhibited.
The advanced oxidation technologies (AOPs) can generate free radicals and other substances with strong oxidation activity in the reaction process, so that the advanced oxidation technologies have a relatively obvious effect on removing refractory organic pollutants and become wastewater treatment technologies with wide application prospects. In the advanced oxidation treatment process, organic substances can be generated by free radical active oxide generated in the reaction processDegraded into low-toxicity or non-toxic small-molecule compounds and even can be completely mineralized into CO2And H2And O. Fenton reaction (Fenton) is a typical hydroxyl radical (HO) using hydrogen peroxide as an oxidizing agent·,E02.8V) advanced oxidation technology (HO) as the main active species·AOPs) are widely used in wastewater treatment and exhibit many advantages in wastewater treatment processes, such as high efficiency, simple operation, safe and nontoxic oxidizing agents, and the like. Ozone oxidation (E)02.07V) degrades pollutants mainly through two routes of direct oxidation and hydroxyl radical oxidation, which has been widely used for degradation of organic pollutants as a typical advanced oxidation technology. However, the technology has the problems of selective oxidation, incomplete oxidation, low ozone utilization efficiency and the like in the application process. Sulfate radical (SO) generated after persulfate is activated4 ·-) The catalyst shows stronger oxidizability under neutral conditions, and is more beneficial to the effective degradation of pollutants. In general, advanced oxidation technologies (AOPs) based on hydrogen peroxide, ozone and persulfate as oxidants for water treatment have great application prospects in wastewater treatment.
In the last two decades, the electrochemical advanced oxidation technology has attracted extensive attention in the field of wastewater treatment due to its characteristics of high efficiency, environmental friendliness, versatility, and the like. However, some drawbacks of the two-dimensional electrode electrochemical process limit its practical application in wastewater treatment. In contrast, the three-dimensional electrode reactor has the advantages of large electrode contact area, low energy consumption, high mass transfer rate and the like, and thus the three-dimensional electrode reactor is a research hotspot in the water treatment direction. CN 106396030A discloses a method for treating printing and dyeing wastewater by using three-dimensional electrode-electro-Fenton coupling, which takes an iron plate or an iron net as an anode, a porous carbon electrode as a cathode, and binary mixed particles of activated carbon and nano iron as a third electrode, applies direct current for stabilizing pressure, and carries out wastewater treatment under the conditions of aeration and stirring. The method utilizes the Fe produced by the anode2+Reacting with hydrogen peroxide generated by a cathode to generate hydroxyl radicals, then utilizing the hydroxyl radicals to react with organic matters in the printing and dyeing wastewater to realize the purpose of removing pollutants, and using third electricityActive carbon and nano iron particles in the electrode play a role in electric conduction, and the nano iron particles assist the iron anode to generate Fe2+As the reaction proceeds, the nano-iron particles are gradually lost, and the third electrode is difficult to reuse, which hinders the reduction of the wastewater treatment cost. Moreover, the method can generate a large amount of iron sludge in the wastewater treatment process, is not beneficial to realizing sludge-water separation, and needs subsequent treatment and disposal of the sludge, thereby increasing the wastewater treatment cost. In addition, although aeration can promote the generation of hydrogen peroxide at the cathode and accelerate the generation of hydroxyl radicals in the electro-fenton process, the types and the number of the radicals generated in this way are limited, and the pollutant degradation efficiency and the degradation effect are still to be improved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for treating refractory wastewater by coupling an oxidant with a three-dimensional electrode, so that the degradation efficiency and the degradation effect of the refractory wastewater are effectively improved while the wastewater treatment cost is reduced.
The invention provides a method for treating refractory wastewater by using a three-dimensional electrode coupling oxidant, which comprises the following steps:
adding refractory wastewater to be treated with the pH value of 3-11 into a wastewater treatment container with a plate-type anode and a plate-type cathode, adding an oxidant and a particle electrode into the wastewater treatment container, stirring to enable the particle electrode to be in a fluidized state, starting a direct current power supply connected with the plate-type anode and the plate-type cathode, and controlling the current density to be 2-20 mA/cm2Treating for 15-60 min under the condition of (1), and finishing the treatment of the refractory wastewater;
the particle electrode is a magnetic spinel ferrite MFe2O4The addition amount of the particle electrode is 0.3-30 g per liter of wastewater, and the oxidant is at least one of persulfate, hydrogen peroxide and ozone.
In the method for treating refractory wastewater by coupling the three-dimensional electrode with the oxidant, the persulfate is peroxydisulfate or peroxymonosulfate.
In the method for treating the refractory wastewater by using the three-dimensional electrode coupling oxidant, the addition amount of persulfate or hydrogen peroxide is 1-20 mmol per liter of wastewater, and the introduction amount of ozone is 100-1000 mL/min.
In the method for treating refractory wastewater by using three-dimensional electrode coupled oxidant, the magnetic spinel type ferrite MFe2O4The nanoparticles are preferably CuFe2O4、CoFe2O4、ZnFe2O4、MnFe2O4、NiFe2O4At least one of the nanoparticles.
In the method for treating the refractory wastewater by the three-dimensional electrode coupling oxidant, the distance between the plate type anode and the plate type cathode is comprehensively determined according to the anode and cathode materials, the volume of the wastewater treatment container, the adopted hydraulic conditions and other factors, so that the principle of reducing the energy consumption of the reaction process and improving the current efficiency as much as possible on the basis of meeting the pollutant removal effect is taken as a principle. The distance between the plate type anode and the plate type cathode is at least 10mm, and the distance between the plate type anode and the plate type cathode is preferably 40-100 mm.
In the method for treating refractory wastewater by using the three-dimensional electrode coupling oxidant, the pH value of wastewater to be treated is 3-11, the specific pH value of the wastewater to be treated is determined by the type of the oxidant added in the later stage, and in order to achieve a better wastewater treatment effect, generally, when the oxidant is hydrogen peroxide, the pH value of the wastewater to be treated is 3-5, when the oxidant is persulfate, the pH value of the wastewater to be treated is 2-10, when the oxidant is ozone, the pH value of the wastewater to be treated is 4-11, when the hydrogen peroxide and the persulfate are used in combination, the preferred pH value of the wastewater to be treated is 3-5, when the ozone and the persulfate are used in combination, the preferable pH value of the wastewater to be treated is 4-10, when the ozone and the hydrogen peroxide are used in combination or the three oxidants are used in combination, the preferable pH value of the wastewater to be treated is 4-5. In order to make the pH value of the wastewater to be treated reach the above specific pH value range, the pH value of the wastewater may need to be adjusted by using dilute acid (hydrochloric acid, dilute sulfuric acid) or dilute alkali (sodium hydroxide, ammonia water) according to the water quality condition of the wastewater to be treated.
According to the method for treating the degradation-resistant wastewater by the three-dimensional electrode coupling oxidant, according to the condition of the electrolyte content in the wastewater to be treated, the electrolyte may need to be added into the wastewater in the step (1) before the pH value of the wastewater is adjusted, whether the electrolyte needs to be added and the addition amount of the electrolyte are determined according to the actual water quality condition of the wastewater to be treated, the electrolyte content in the wastewater to be treated is determined on the basis of ensuring that the electrolytic reaction generates stable required current, the concentration is not too high, the effects of preventing the generation of bypass current and short-circuit current and inhibiting the electrochemical reaction are avoided, and the chlorine salt is avoided being selected as the electrolyte. Typically, the electrolyte is added in an amount of not more than 50mmol per liter of wastewater.
The plate anode and the plate cathode are made of stainless steel, graphite, titanium, nickel and composite metal oxide, and the specific structures of the plate anode and the plate cathode can be plate-shaped or net-shaped.
In the method for treating the refractory wastewater by using the three-dimensional electrode coupling oxidant, the particle size of the particle electrode is nano-scale, and the preferable particle size range is 10-100 nm.
In the method for treating the refractory wastewater by the three-dimensional electrode coupling oxidant, the particle electrodes are in a fluidized state by stirring in the step (2), and the stirring speed is determined according to the particle diameter of the particle electrodes and the treatment capacity of the wastewater.
The principle of the method of the invention is as follows:
the invention adopts the three-dimensional electrode to degrade the difficultly degradable wastewater, because the electrochemical reaction of the three-dimensional electrode reactor is carried out on the surface of the main electrode and the surface of the particle electrode, the particle electrode is polarized into the miniature electrolytic cell with positive electricity at one end and negative electricity at the other end under the action of an electric field, the mass transfer distance can be greatly shortened, the specific surface area of the electrochemical reaction process is increased, and the number of active sites is increased. More importantly, the invention adopts CuFe2O4、CoFe2O4、ZnFe2O4、MnFe2O4、NiFe2O4Isomagnetic spinel type ferrite MFe2O4The nanometer particles are used as particle electrodes, and one or a combination of more of persulfate, hydrogen peroxide and ozone is addedAnd in the process of introducing direct current to treat wastewater, the particle electrode plays a dual role of a third electrode and a catalyst. On one hand, the surface of the particle electrode is charged, and the same electrochemical reaction with the main electrode plate can occur on the surface of the particle electrode, namely hydroxyl radicals are generated at the anode of the micro particle electrode, and active substances such as peroxide hydroxide or sulfate radicals are generated at the cathode, so that the number of radicals in a reaction system is increased; on the other hand, the particle electrode chemically reacts with an oxidizing agent as a catalyst to generate radicals by a catalytic oxidation process, specifically, MFe2O4The catalyst can activate hydrogen peroxide and ozone to generate hydroxyl free radicals and activate persulfate to generate sulfate free radicals. Under the effect of the particle electrode and the added oxidant, the synergistic effect advantage of electrochemistry and catalytic oxidation can be greatly played, the types of free radicals are increased, the generation of the free radicals is promoted through various paths, the number of the free radicals is effectively increased, the degradation of organic pollutants is accelerated, the removal rate and the mineralization rate of the pollutants are effectively increased, and the wastewater treatment efficiency is increased. In addition, the present invention employs a magnetic spinel-type ferrite MFe2O4The nanometer particles are used as particle electrodes, have good stability and low loss in the wastewater treatment process, can be repeatedly used, and are beneficial to improving the utilization rate of materials, because the MFe2O4The nano particles have magnetism, so that the separation of the nano particles in wastewater is easy to realize, and the economic cost of the process is reduced.
Compared with the prior art, the invention has the following beneficial technical effects:
1. the invention provides a method for treating refractory wastewater by using a three-dimensional electrode coupling oxidant, which adopts CuFe2O4、CoFe2O4、ZnFe2O4、MnFe2O4、NiFe2O4Isomagnetic spinel type ferrite MFe2O4On the basis that the nano particles are used as particle electrodes, at least one of oxidants of persulfate, hydrogen peroxide and ozone is added to degrade the wastewater, and the wastewater is degraded when the main electrode plate is electrified and the particle electrodes are in a fluidized stateIn the treatment process, the particle electrode plays a role in the third electrode and the catalyst, so that the synergistic effect of an electrochemical process and a catalytic oxidation reaction in a system is greatly enhanced, the types of free radicals are effectively increased, the generation of the free radicals is promoted through various paths, the number of the free radicals is effectively increased, the activation efficiency of an oxidant is enhanced, the degradation of organic pollutants is accelerated, and compared with the prior art, the method provided by the invention can effectively increase the removal rate and the mineralization rate of the pollutants and simultaneously effectively improve the wastewater treatment efficiency.
2. In the method for treating refractory wastewater by using the three-dimensional electrode coupling oxidant, the adopted particle electrode has good stability and low loss in the wastewater treatment process, can be repeatedly used, is favorable for improving the utilization rate of materials, does not increase the amount of iron sludge, has low difficulty in separating mud from water, and has MFe (MFe)2O4The nanometer particles have magnetism, so that the separation of the nanometer particles in the wastewater is easy to realize, the factors are favorable for reducing the treatment difficulty of the wastewater difficult to degrade, and the economic cost of the process is effectively reduced.
3. Experiments show that when the method is used for treating the simulated wastewater with the concentration of the pollutants difficult to degrade being 10-400 mg/L, the degradation rate of the organic matters in the simulated wastewater reaches 95%, 97% or even more than 99% under the condition that the wastewater treatment time is 15-50 min, and the method has the characteristics of high degradation efficiency and good degradation effect.
4. The method provided by the invention has the characteristics of simple operation, low process cost and easy realization of popularization and application.
Drawings
FIG. 1 is a schematic diagram of the present invention for treating refractory wastewater by using three-dimensional electrode coupled oxidant.
Fig. 2 is a graph comparing the removal effect of contaminants in example 1 and comparative example 1.
Detailed Description
The method for treating refractory wastewater by using three-dimensional electrode coupling oxidant provided by the invention is further explained by the following examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and those skilled in the art can make certain insubstantial modifications and adaptations of the present invention based on the above disclosure and still fall within the scope of the present invention.
Example 1
In this example, an atrazine (ATZ, chemical name is 2-chloro-4-diethylamino-6-isopropylamino-1, 3, 5-triazine) solution with a concentration of 10mg/L, pH adjusted to 6.3 is used as simulated wastewater, which illustrates the method for treating refractory wastewater by using a three-dimensional electrode coupling oxidant provided by the present invention, and the steps are as follows:
(1) placing two electrode plates with the size of 5cm multiplied by 11cm in a wastewater treatment container, wherein the two electrode plates are opposite and parallel to each other and are connected with a direct current power supply, and the anode plate is a composite metal oxide Ti/RuO2-IrO2The plate, the negative plate is stainless steel plate, and the polar plate interval of positive plate and negative plate is 57 mm. 200mL of simulated wastewater was added to the wastewater treatment vessel in which the anode and cathode plates were arranged.
(2) Adding copper ferrite (CuFe) with particle size of about 20nm into a wastewater treatment container2O4CFO) particles, the addition of the CFO particles is 3g per liter of simulated wastewater, then sodium Peroxodisulfate (PS) is added according to the amount of 4mmol per liter of simulated wastewater, the simulated wastewater is mechanically stirred at the rotating speed of 300rpm to enable the CFO particles to be in a fluidized state, a direct current power supply is started, and the current density is 4mA/cm2The simulated wastewater is treated for 35min under the condition of (1), namely the treatment of the simulated wastewater is completed, the direct-current power supply is turned off, and the stirring is stopped. During the process of treating the simulated wastewater, sampling every 5min to determine the concentration of ATZ, and the result shows that more than 99% of ATZ in the simulated wastewater is removed after treatment in a three-dimensional electrode coupling oxidant peroxodisulfate system (EC/CFO/PS) for 35 min.
Comparative example 1
For comparison with example 1, this comparative example treated a simulated wastewater having an ATZ concentration of 10mg/L in the same manner as in example 1. The process of this comparative example is essentially the same as example 1, except that no PS is added to this comparative example. During the process of treating the simulated wastewater, sampling every 5min to determine the concentration of ATZ, and the result shows that only 21 percent of ATZ is removed after 35min treatment in a three-dimensional electrode system (EC/CFO).
FIG. 2 is a graph comparing the removal effects of contaminants in example 1 and comparative example 1, in which the ordinate [ ATZ ]]/[ATZ]0The ratio of the ATZ concentration in the sampled sample to the initial ATZ concentration of the simulated wastewater is shown, with curve EC/CFO/PS representing example 1 and curve EC/CFO representing comparative example 1. As can be seen from FIG. 2, the method of the present invention adds the oxidizing agent on the basis of adding the particle electrode, which can significantly improve the degradation efficiency of the organic matters in the simulated wastewater, the water quality condition after the simulated wastewater is treated for 10min in example 1 is equivalent to the water quality condition after the simulated wastewater is treated for 35min in comparative example 1, and after the simulated wastewater is treated for 35min, ATZ in the simulated wastewater of example 1 is substantially completely removed, while the ATZ removal rate in comparative example 1 is only 21%.
Example 2
In this example, sulfamethoxazole (SMX, chemical name of 4-amino-N- (5-methyl-3-isoxazolyl) benzenesulfonamide) solution adjusted to a concentration of 7.0 at 10mg/L, pH is used as simulated wastewater to illustrate the method for treating refractory wastewater by using three-dimensional electrode coupling oxidant provided by the present invention, the steps are as follows:
(1) two electrode plates with the size of 5cm multiplied by 11cm are arranged in a wastewater treatment container, the two electrode plates are opposite to each other, are parallel to each other and are connected with a direct current power supply, wherein an anode plate is a nickel plate, a cathode plate is a stainless steel plate, and the distance between the anode plate and the cathode plate is 65 mm. 200mL of simulated wastewater was added to a wastewater treatment vessel in which an anode plate and a cathode plate were arranged, followed by addition of Na as an electrolyte2SO4，Na2SO4The amount of addition of (D) is 10mmol per liter of wastewater.
(2) Adding zinc ferrite (ZnFe) with the particle size of about 20nm into a waste water treatment container2O4ZFO) particles, ZFO particles are added in an amount of 0.3g per liter of simulated wastewater, potassium hydrogen Peroxymonosulfate (PMS) is added in an amount of 1mmol per liter of simulated wastewater, the simulated wastewater is mechanically stirred at a rotating speed of 300rpm to enable ZFO particles to be in a fluidized state, a direct current power supply is started, and the current density is 2mA/cm2Treating the simulated wastewater for 15min under the condition of (1),thus completing the treatment of the simulated wastewater. And (3) turning off a direct current power supply, stopping stirring, sampling and carrying out SMX concentration detection, wherein the results show that more than 99% of SMX in the simulated wastewater is removed after treatment for 15min in a three-dimensional electrode coupling oxidant-permonosulfate system (EC/ZFO/PMS).
Example 3
In this example, a 2, 4-dinitrophenol (2,4-DNP) solution with a concentration of 50mg/L, pH adjusted to 7.0 is used as simulated wastewater to illustrate the method for treating refractory wastewater by using a three-dimensional electrode-coupled oxidant provided by the present invention, which comprises the following steps:
(1) two electrode plates with the size of 5cm multiplied by 11cm are arranged in a wastewater treatment container, the two electrode plates are opposite to each other and are parallel to each other and are connected with a direct current power supply, wherein an anode plate is a titanium plate, a cathode plate is a graphite plate, and the distance between the anode plate and the cathode plate is 80 mm. 200mL of simulated wastewater was added to the wastewater treatment vessel in which the anode and cathode plates were arranged.
(2) Adding manganese ferrite (MnFe) with the particle size of about 20nm into a waste water treatment container2O4MFO) particles, the MFO particles being added in an amount of 4g per liter of simulated wastewater, sodium Peroxodisulfate (PS) being added in an amount of 4mmol per liter of simulated wastewater, the simulated wastewater being mechanically stirred at 300rpm to bring the MFO particles into a fluidized state, a DC power supply being turned on at a current density of 4mA/cm2The simulated wastewater is treated for 20min under the condition of (1), and then the treatment of the simulated wastewater is completed. And (3) turning off a direct current power supply, stopping stirring, sampling and carrying out 2,4-DNP concentration detection, wherein the results show that more than 99% of 2,4-DNP in the simulated wastewater is removed after treatment in a three-dimensional electrode coupling oxidant peroxodisulfate system (EC/MFO/PS) for 20 min.
Example 4
In this example, a 4-nitrophenol (PNP) solution with a concentration of 200mg/L, pH adjusted to 3.0 is used as simulated wastewater to illustrate the method for treating refractory wastewater by using a three-dimensional electrode coupling oxidant provided by the present invention, and the steps are as follows:
(1) placing two electrode plates with the size of 5cm multiplied by 11cm in a wastewater treatment container, wherein the two electrode plates are opposite and parallel to each other and are connected with a direct current power supply, and the two electrode plates are connected with the direct current power supplyIn the anode plate and the cathode plate are both composite metal oxide Ti/RuO2-IrO2The distance between the anode plate and the cathode plate is 60 mm. 200mL of simulated wastewater was added to a wastewater treatment vessel in which an anode plate and a cathode plate were arranged, followed by addition of Na as an electrolyte2SO4，Na2SO4The amount of addition of (D) was 45mmol per liter of wastewater.
(2) Adding copper ferrite (CuFe) with particle size of about 10nm into a wastewater treatment container2O4CFO), the CFO particles were added in an amount of 10g per liter of simulated wastewater, and then hydrogen peroxide (H) was added in an amount of 15mmol per liter of simulated wastewater2O2) Mechanically stirring the simulated wastewater at the rotating speed of 250rpm to enable the CFO particles to be in a fluidized state, starting a direct-current power supply, and controlling the current density to be 10mA/cm2The simulated wastewater is treated for 50min under the condition of (1), and then the treatment of the simulated wastewater is completed. Closing the direct current power supply, stopping stirring, sampling and carrying out PNP concentration detection, wherein the result shows that an oxidant hydrogen peroxide system (EC/CFO/H) is coupled at the three-dimensional electrode2O2) Middle treatment for 50min, simulating that 95% of the PNP in the wastewater is removed.
Example 5
In this embodiment, a rhodamine b (rhb) solution with a concentration of 200mg/L, pH adjusted to 10.0 is used as the simulated wastewater, which illustrates the method for treating refractory wastewater by using the three-dimensional electrode coupling oxidant provided by the present invention, and the steps are as follows:
(1) placing two electrode plates with the size of 5cm multiplied by 11cm in a wastewater treatment container, wherein the two electrode plates are opposite and parallel to each other and are connected with a direct current power supply, and the anode plate and the cathode plate are both composite metal oxide Ti/RuO2-IrO2And the distance between the anode plate and the cathode plate is 55 mm. 200mL of simulated wastewater was added to a wastewater treatment vessel in which an anode plate and a cathode plate were arranged, followed by addition of Na as an electrolyte2SO4，Na2SO4The amount of addition of (D) was 50mmol per liter of wastewater.
(2) Adding cobalt ferrite (CoFe) with a particle size of about 100nm to a wastewater treatment vessel2O4) The amount of cobalt ferrite particles added is 15g per liter of simulated wastewater, and thenContinuously introducing ozone (O) at a flow rate of 200mL/min3) Mechanically stirring the simulated wastewater at the rotating speed of 600rpm to ensure that the cobalt ferrite particles are in a fluidized state, starting a direct current power supply, and controlling the current density to be 8mA/cm2The simulated wastewater is treated for 30min under the condition of (1), and then the treatment of the simulated wastewater is completed. And (3) closing the direct-current power supply, stopping stirring, sampling and carrying out PNP concentration detection, wherein the result shows that 98% of RhB in the simulated wastewater is removed after treatment for 30min in a three-dimensional electrode coupling oxidant ozone system.
Example 6
In this example, a phenol solution with a concentration of 400mg/L is used as simulated wastewater (without adjusting the pH value of the phenol solution), which illustrates the method for treating refractory wastewater by using a three-dimensional electrode coupling oxidant provided by the present invention, the steps are as follows:
(1) placing two electrode plates with the size of 5cm multiplied by 11cm in a wastewater treatment container, wherein the two electrode plates are opposite and parallel to each other and are connected with a direct current power supply, and the anode plate is a composite metal oxide Ti/RuO2-IrO2The plate, the negative plate is the graphite plate, and the polar plate interval of positive plate and negative plate is 50 mm. 250mL of simulated wastewater was added to a wastewater treatment vessel in which an anode plate and a cathode plate were arranged, followed by addition of electrolyte Na2SO4，Na2SO4The amount of addition of (D) was 50mmol per liter of wastewater.
(2) Adding copper ferrite (CuFe) with particle size of about 50nm into a waste water treatment container2O4CFO) particles added in an amount of 30g per liter of simulated wastewater, and hydrogen peroxide (H) added in an amount of 15mmol per liter of wastewater2O2) Adding Peroxodisulfate (PS) in an amount of 10 mmol/L wastewater, mechanically stirring the simulated wastewater at 500rpm to fluidize the CFO particles, turning on a DC power supply, and controlling the current density at 20mA/cm2The simulated wastewater is treated for 30min under the condition of (1), and then the treatment of the simulated wastewater is completed. And (3) closing the direct-current power supply, stopping stirring, sampling and detecting the concentration of phenol, wherein the result shows that 97% of phenol in the simulated wastewater is removed after treatment for 30min in a three-dimensional electrode coupling oxidant hydrogen peroxide and persulfate system.
Example 7
In this example, a Dimethylacetamide (DMAC) solution with a concentration of 200mg/L is used as simulated wastewater (without adjusting the pH of the DMAC solution), which illustrates the method for treating refractory wastewater by using a three-dimensional electrode coupling oxidant provided by the present invention, and the steps are as follows:
(1) two electrode plates with the size of 5cm multiplied by 11cm are arranged in a wastewater treatment container, the two electrode plates are opposite to each other, are parallel to each other and are connected with a direct current power supply, wherein an anode plate is a nickel plate, a cathode plate is a graphite plate, and the distance between the anode plate and the cathode plate is 97 mm. 250mL of simulated wastewater was added to a wastewater treatment vessel in which an anode plate and a cathode plate were arranged, followed by addition of electrolyte Na2SO4，Na2SO4The amount of addition of (D) was 50mmol per liter of wastewater.
(2) Adding nickel ferrite (NiFe) with the particle size of about 30nm into a wastewater treatment container2O4) The nickel ferrite particles were added in an amount of 25g per liter of simulated wastewater, and then hydrogen peroxide (H) was added in an amount of 10mmol per liter of wastewater2O2) And continuously introducing O at a flow rate of 100mL/min3Mechanically stirring the simulated wastewater at the rotating speed of 400rpm to ensure that the nickel ferrite particles are in a fluidized state, starting a direct current power supply, and controlling the current density to be 8mA/cm2The simulated wastewater is treated for 40min under the condition of (1), and then the treatment of the simulated wastewater is completed. And (3) closing the direct current power supply, stopping stirring, sampling and carrying out DMAC concentration detection, wherein the result shows that more than 99% of DMAC in the simulated wastewater is removed after the DMAC is treated for 30min in a three-dimensional electrode coupling oxidant ozone and hydrogen peroxide system.
Claims (7)
1. A method for treating refractory wastewater by three-dimensional electrode coupling oxidant is characterized by comprising the following steps:
adding refractory wastewater to be treated with the pH value of 3-11 into a wastewater treatment container with a plate-type anode and a plate-type cathode, adding an oxidant and a particle electrode into the wastewater treatment container, stirring to enable the particle electrode to be in a fluidized state, starting a direct current power supply connected with the plate-type anode and the plate-type cathode, and controlling the current density to be 2-20 mA/cm2Under the conditions ofTreating for 15-50 min to complete the treatment of the refractory wastewater;
the particle electrode is a magnetic spinel ferrite MFe2O4Nanoparticle, magnetic spinel type ferrite MFe2O4The nano-particles are CuFe2O4、CoFe2O4、ZnFe2O4、MnFe2O4、NiFe2O4At least one of nano particles, wherein the addition amount of the particle electrode is 0.3-30 g per liter of wastewater; the oxidant is at least one of persulfate and hydrogen peroxide, and the addition amount of the persulfate or the hydrogen peroxide is 1-20 mmol per liter of wastewater.
2. The method for treating refractory wastewater by using a three-dimensional electrode coupled oxidant as claimed in claim 1, wherein the plate spacing between the plate anode and the plate cathode is at least 10 mm.
3. The method for treating refractory wastewater by using the three-dimensional electrode coupled oxidant as claimed in claim 2, wherein the distance between the plate anode and the plate cathode is 40-100 mm.
4. The method of claim 1, wherein the electrolyte is added to the wastewater before the oxidizing agent and the particle electrode are added to the wastewater.
5. The method for treating refractory wastewater by using three-dimensional electrode-coupled oxidant according to claim 4, wherein the addition amount of the electrolyte is not more than 50mmol per liter of wastewater.
6. The method for treating refractory wastewater by using the three-dimensional electrode coupled oxidant as claimed in claim 1, wherein the plate-type anode and the plate-type cathode are made of stainless steel, graphite, titanium, nickel or composite metal oxide.
7. The method for treating refractory wastewater by using the three-dimensional electrode coupled oxidant as claimed in claim 1, wherein the particle size of the particle electrode is 10-100 nm.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN202508947U (en) * | 2012-03-08 | 2012-10-31 | 郑州宇通重工有限公司 | Device for advanced wastewater treatment |
| CN103539234A (en) * | 2013-11-06 | 2014-01-29 | 中国海洋石油总公司 | Integrated processing method of fracturing flow-back fluid |
| CN203545827U (en) * | 2013-11-06 | 2014-04-16 | 中国海洋石油总公司 | Three-dimensional electrode-ultrasonic-oxidative coupling reactor |
| CN105253960A (en) * | 2015-11-23 | 2016-01-20 | 雅本化学股份有限公司 | Wastewater treatment device and method for treating wastewater by adopting wastewater treatment device |
| CN205076873U (en) * | 2015-09-22 | 2016-03-09 | 东莞市中金环保科技有限公司 | Novel three -dimensional electrode biomembrane waste water treatment device |
| CN107459233A (en) * | 2017-10-12 | 2017-12-12 | 齐鲁理工学院 | A kind of water treatment system and method for three-dimensional class electricity Fenton processing triclocarban |
| CN107459232A (en) * | 2017-10-12 | 2017-12-12 | 齐鲁理工学院 | A kind of water treatment system and method for three-dimensional class electricity Fenton degraded naproxen |
-
2018
- 2018-08-20 CN CN201810949004.2A patent/CN108928890B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN202508947U (en) * | 2012-03-08 | 2012-10-31 | 郑州宇通重工有限公司 | Device for advanced wastewater treatment |
| CN103539234A (en) * | 2013-11-06 | 2014-01-29 | 中国海洋石油总公司 | Integrated processing method of fracturing flow-back fluid |
| CN203545827U (en) * | 2013-11-06 | 2014-04-16 | 中国海洋石油总公司 | Three-dimensional electrode-ultrasonic-oxidative coupling reactor |
| CN205076873U (en) * | 2015-09-22 | 2016-03-09 | 东莞市中金环保科技有限公司 | Novel three -dimensional electrode biomembrane waste water treatment device |
| CN105253960A (en) * | 2015-11-23 | 2016-01-20 | 雅本化学股份有限公司 | Wastewater treatment device and method for treating wastewater by adopting wastewater treatment device |
| CN107459233A (en) * | 2017-10-12 | 2017-12-12 | 齐鲁理工学院 | A kind of water treatment system and method for three-dimensional class electricity Fenton processing triclocarban |
| CN107459232A (en) * | 2017-10-12 | 2017-12-12 | 齐鲁理工学院 | A kind of water treatment system and method for three-dimensional class electricity Fenton degraded naproxen |
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