High-efficiency heterogeneous Fenton catalytic reaction system based on quartz refractory wastewater and application of high-efficiency heterogeneous Fenton catalytic reaction system

Abstract

The invention discloses an efficient multi-phase Fenton catalytic reaction system based on quartz refractory wastewater. The system sequentially comprises a water inlet tank, a catalytic reduction tower, a multi-phase Fenton catalytic oxidation pond, a neutralization degassing pond, a flocculation pond and an inclined plate sedimentation pond in the wastewater treatment direction. The bottoms of the catalytic reduction tower and the multi-phase Fenton catalytic oxidation pond are loaded with micro-electrolysis filler; aeration pipes are arranged at the bottoms of the catalytic reduction tower and the multi-phase Fenton catalytic oxidation pond, and an aeration pump is connected with the aeration pipes to provide a gas source for the catalytic reduction tower and the multi-phase Fenton catalytic oxidation pond. According to the method, a catalytic reduction process is added before Fenton oxidation, stable macromolecular organic matters in the wastewater in the quartz industry are subjected to chain scission and thorough oxidation in sequence, the average removal rate of COD (Chemical Oxygen Demand) stably exceeds 50%, and efficient and deep removal of degraded organic matters in the wastewater is realized, the dosage of chemicals is reduced, and the sludge yield is reduced.

Description

Technical Field

[0001] This invention relates to the field of wastewater treatment technology, and in particular to a highly efficient multiphase Fenton catalytic reaction system for quartz-recalcitrant wastewater and its application. Background Technology

[0002] Industrial wastewater generated by the quartz industry, especially the deep processing of quartz sand, typically contains a large amount of quartz sand particles, suspended solids, acidic or alkaline pollutants, or other pollutants and chemical oxygen demand. It contains complex organic matter, multiple bonds, high carbon chains, and azo compounds. Currently, the main methods for treating wastewater from the quartz industry include physical adsorption, chemical precipitation, and advanced oxidation. However, ordinary biochemical treatment processes have low degradation efficiency and are difficult to meet increasingly stringent emission standards.

[0003] Fenton oxidation refers to the homogeneous catalytic reaction between ferrous ions and hydrogen peroxide under acidic conditions, which produces highly oxidizing hydroxyl radicals. The hydroxyl radicals directly oxidize and decompose organic pollutants in water into CO2 and water. Although Fenton technology has strong oxidation capacity, it has the following defects: (1) A large amount of iron sludge is generated after the homogeneous reaction, causing secondary pollution and high sludge disposal costs; (2) The ability to open and break the chain of complex macromolecular pollutants is limited, resulting in incomplete oxidation efficiency; (3) The amount of reagent consumed is large and the operating cost is high; (4) The ability to resist water quality shock load is weak.

[0004] Existing technologies have attempted to combine catalytic reduction and oxidation, but these typically suffer from complex processes and unstable catalytic efficiency. Furthermore, they exhibit poor adaptability to wastewater from the quartz industry, particularly wastewater containing specific silicates and organic additives. Therefore, there is an urgent need to develop a highly efficient, stable, low-cost, and specifically tailored advanced treatment technology for the water quality characteristics of the quartz industry. Summary of the Invention

[0005] The technical problem to be solved by this invention is to overcome the shortcomings of the prior art and solve the problem of poor adaptability in the treatment of wastewater in the quartz industry. Traditional Fenton oxidation has problems such as secondary pollution, incomplete oxidation, and large consumption of reagents. Based on the above, a high-efficiency multiphase Fenton catalytic reaction system based on refractory quartz wastewater and its application are proposed.

[0006] To achieve the above objectives, the present invention adopts the following technical solution: A high-efficiency multiphase Fenton catalytic reaction system based on quartz recalcitrant wastewater, the system comprising, in sequence along the wastewater treatment direction, an inlet tank, a catalytic reduction tower, a multiphase Fenton catalytic oxidation tank, a neutralization and degassing tank, a flocculation tank and an inclined plate sedimentation tank; Both the catalytic reduction tower and the multiphase Fenton catalytic oxidation tank are filled with micro-electrolysis packing at the bottom. The bottom of the catalytic reduction tower and the multiphase Fenton catalytic oxidation tank are equipped with aeration pipes, which are connected to the aeration pipes by an aeration pump to provide gas to the catalytic reduction tower and the multiphase Fenton catalytic oxidation tank.

[0007] Preferably, the catalytic reduction tower is composed of a single-stage reduction tower or multiple-stage reduction towers connected in series.

[0008] Preferably, the micro-electrolysis filler includes iron, carbon, a noble metal catalyst, and a surface activator.

[0009] Preferably, the surfactant is sodium tripolyphosphate, sodium dodecylbenzenesulfonate, and N,N-dimethylformate in a mass ratio of 3-5:10-12:2-3.

[0010] The present invention also provides a method for treating quartz-recalcitrant wastewater using the above-described system, comprising the following steps: (1) Place the micro-electrolysis packing material at the bottom of the catalytic reduction tower and the multiphase Fenton catalytic oxidation tank; (2) The wastewater is temporarily stored in the inlet tank, and after the pH is adjusted with sulfuric acid, the wastewater is transported to the inlet of the catalytic reduction tower; (3) Aeration is carried out using an aeration pump at the bottom of the catalytic reduction tower; (4) The wastewater after catalytic reduction treatment is then subjected to catalytic oxidation reaction in a multiphase Fenton catalytic oxidation tank; (5) Wastewater treated by the multiphase Fenton catalytic oxidation tank enters the neutralization and degassing tank, and alkali solution is added to adjust the pH to neutral or weakly alkaline. (6) The water treated in the neutralization and degassing tank enters the flocculation tank for further treatment; (7) The effluent treated by the flocculation tank enters the inclined plate sedimentation tank, and water samples are collected from the outlet of the inclined plate sedimentation tank for analysis and testing.

[0011] Preferably, in step (2), the pH is adjusted to 2.5-2.6.

[0012] Preferably, the micro-electrolysis filler comprises iron, carbon, noble metal catalysts and surfactants, and its particle size is 2-3 cm.

[0013] Preferably, hydrogen peroxide and ferrous sulfate are added to the multiphase Fenton catalytic oxidation tank, wherein the mass concentration of hydrogen peroxide is 27.5% and the mass concentration of ferrous sulfate is 10%; the alkaline solution added to the neutralization and degassing tank is sodium hydroxide with a mass concentration of 30%.

[0014] Preferably, the carbon is graphene or coke.

[0015] By adopting the above technical solution, the present invention has the following beneficial effects compared with the prior art: This invention achieves the first chain breaking and then complete oxidation of stable macromolecular organic matter in quartz industry wastewater by setting up a multi-stage catalytic reduction process before Fenton oxidation. Combined with electrocatalytic treatment, the wastewater is treated to achieve an average COD removal rate of over 50%, realizing efficient and deep removal of degraded organic matter in wastewater, reducing the amount of reagents used and the amount of sludge produced.

[0016] This invention treats wastewater by combining single-stage or multi-stage reduction tower catalytic reduction with multiphase Fenton catalytic oxidation tank, effectively solving the problem of sludge treatment in wastewater. Moreover, the micro-electrolysis packing has a low annual loss rate, while reducing the amount of iron salt added, reducing the generation of iron sludge, effectively preventing caking and passivation problems, realizing waste-to-waste treatment, and reducing the cost of wastewater treatment.

[0017] This invention reduces the concentration fluctuation of quartz plant wastewater and improves system stability by combining a catalytic reduction tower and a multiphase Fenton catalytic oxidation tank. The process flow is clear, and automation can be achieved by controlling key parameters to ensure that the effluent quality consistently meets standards. Attached Figure Description

[0018] Figure 1 , Figure 2 This is a schematic diagram of a high-efficiency multiphase Fenton catalytic reaction system based on quartz recalcitrant wastewater according to the present invention.

[0019] Figure 3 This is a schematic diagram of the catalytic reduction tower of the present invention, wherein 1 is the micro-electrolysis packing layer.

[0020] Figure 4 This is a schematic diagram of COD removal rate in a single-stage catalytic reduction tower mode.

[0021] Figure 5 This is a schematic diagram of the COD removal rate in a multi-stage catalytic reduction tower mode.

[0022] Figure 6 This is a schematic diagram of COD removal rate in the non-catalytic reduction tower mode. Detailed Implementation

[0023] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions in the embodiments of this invention will be clearly and completely described below in conjunction with the embodiments of this invention. Obviously, the described embodiments are only some embodiments of this invention, and not all embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0024] A high-efficiency multiphase Fenton catalytic reaction system based on quartz recalcitrant wastewater, the system comprising, in sequence along the wastewater treatment direction, an inlet tank, a catalytic reduction tower, a multiphase Fenton catalytic oxidation tank, a neutralization and degassing tank, a flocculation tank and an inclined plate sedimentation tank; Both the catalytic reduction tower and the multiphase Fenton catalytic oxidation tank are filled with micro-electrolysis packing at the bottom. Both the catalytic reduction tower and the multiphase Fenton catalytic oxidation tank are equipped with aeration pipes at the bottom, which are connected to aeration pumps to provide air to the catalytic reduction tower and the multiphase Fenton catalytic oxidation tank. An acid-adjusting tank is located next to the inlet tank to receive and temporarily store wastewater, and acid is added to the wastewater to precisely adjust the pH value to a strongly acidic range of 2.5-2.6, creating the optimal reaction environment for the subsequent catalytic reduction reaction.

[0025] Preferably, the catalytic reduction tower is composed of a single-stage or multi-stage reduction tower connected in series, and micro-electrolysis packing is set at the bottom of the catalytic reduction tower and the bottom of the multiphase Fenton catalytic oxidation tank for composite catalysis. This enables efficient catalytic reduction of stable pollutants such as multi-bonded, high-carbon skeleton, nitro, and azo compounds in wastewater through ring-opening and chain-breaking reactions, thereby destroying their complex structures and reducing the energy barrier of subsequent oxidation reactions.

[0026] Fenton reagents (hydrogen peroxide and ferrous sulfate) are added to a heterogeneous Fenton catalytic oxidation tank, and under the catalytic action of micro-electrolysis packing, a highly efficient heterogeneous Fenton oxidation occurs.

[0027] Alkaline solution is added to the neutralization and degassing tank to adjust the pH value to neutral or slightly alkaline, so as to terminate Fenton oxidation and promote the precipitation of dissolved iron and the removal of gaseous products.

[0028] Adding flocculants (such as PAM) to the flocculation tank causes the iron sludge and suspended solids to coagulate into large flocs, achieving efficient solid-liquid separation and ultimately producing clear and transparent effluent.

[0029] Preferably, the micro-electrolysis filler comprises iron, carbon, noble metal catalysts and surface activators, and its particle size is 2-3 cm.

[0030] Preferably, the surfactant is sodium tripolyphosphate, sodium dodecylbenzenesulfonate, and N,N-dimethylformate in a mass ratio of 3-5:10-12:2-3.

[0031] The present invention also provides a method for treating refractory quartz wastewater using the above-described system, comprising the following steps: (1) Place the micro-electrolysis packing material at the bottom of the catalytic reduction tower and the multiphase Fenton catalytic oxidation tank; (2) The wastewater is fed through the inlet tank and the pH is adjusted with sulfuric acid before being transported to the inlet of the catalytic reduction tower. By adding sulfuric acid, the pH value of the inlet water is precisely controlled between 2.5 and 2.6.

[0032] (3) Aerate the catalytic reduction tower and the bottom of the multiphase Fenton catalytic oxidation tank unit using aeration pumps; (4) The wastewater treated by the catalytic reduction tower is then reacted in a multiphase Fenton catalytic oxidation tank; the hydraulic retention time is controlled, and for single-stage catalytic reduction, the preferred catalytic reduction reaction time is 1 hour; for two-stage catalytic reduction, the preferred catalytic reduction reaction time is 2 hours. Under the action of the multiphase catalyst, the reduction and ring-opening chain scission of characteristic pollutants are achieved; (5) Wastewater treated by the multiphase Fenton catalytic oxidation tank enters the neutralization and degassing zone, and alkali solution is added to adjust the pH to neutral or weakly alkaline; (6) The water that has undergone neutralization and degassing treatment enters the flocculation tank for further treatment; the flocculant used is anionic PAM. Then it enters the sedimentation tank for solid-liquid separation, and the supernatant is the treated effluent that meets the standards. (7) The effluent treated by the flocculation tank enters the inclined plate sedimentation tank through the inlet, and water samples are collected from the outlet of the inclined plate sedimentation tank for analysis and testing.

[0033] Preferably, in step (2), the pH is adjusted to 2.5-2.6.

[0034] Preferably, the micro-electrolysis filler comprises iron, carbon, noble metal catalysts and surface activators, and its particle size is 2-3 cm.

[0035] Preferably, hydrogen peroxide and ferrous sulfate are added to the multiphase Fenton catalytic oxidation tank, wherein the mass concentration of hydrogen peroxide is 27.5% and the mass concentration of ferrous sulfate is 10%; the alkaline solution added to the neutralization and degassing tank is sodium hydroxide with a mass concentration of 30%.

[0036] Preferably, the carbon is graphene or coke.

[0037] Example 1 A highly efficient multiphase Fenton catalytic reaction system based on quartz recalcitrant wastewater, the system comprising, in sequence along the wastewater treatment direction, an inlet tank, a single-stage catalytic reduction tower, a multiphase Fenton catalytic oxidation tank, a neutralization and degassing tank, a flocculation tank, and an inclined plate sedimentation tank; Both the single-stage catalytic reduction tower and the multiphase Fenton catalytic oxidation tank are filled with micro-electrolysis packing material at the bottom.

[0038] Both the single-stage catalytic reduction tower and the multiphase Fenton catalytic oxidation tank are equipped with aeration pipes at the bottom, which are connected to aeration pumps to provide air to the single-stage catalytic reduction tower and the multiphase Fenton catalytic oxidation tank. An acid-adjusting tank is installed next to the influent tank to receive and temporarily store wastewater, and acid is added to the wastewater to precisely adjust the pH value to a strongly acidic range of 2.5-2.6, creating the optimal reaction environment for subsequent multiphase catalytic reactions.

[0039] Both the single-stage catalytic reduction tower and the multiphase Fenton catalytic oxidation tank are equipped with micro-electrolysis packing at the bottom for composite catalysis. This enables efficient catalytic reduction and ring-opening chain-breaking reactions of stable pollutants in wastewater, such as multi-bonded, high-carbon skeletons, nitro groups, and azo compounds, thereby destroying their complex structures and reducing the energy barrier of subsequent oxidation reactions.

[0040] The micro-electrolysis filler is composed of iron ions, carbon ions, a catalyst (noble metal), and a surfactant, with a particle size of 2-3 cm. The carbon ions in the micro-electrolysis filler are graphene. The surfactants are sodium tripolyphosphate, sodium dodecylbenzenesulfonate, and N,N-dimethylformate in a mass ratio of 3:10:2.

[0041] Fenton reagents (hydrogen peroxide and ferrous sulfate) were added to the heterogeneous Fenton catalytic oxidation tank. The mass concentration of hydrogen peroxide added to the heterogeneous Fenton catalytic oxidation tank was 27.5%, and the mass concentration of ferrous sulfate was 10%. Under the catalytic action of the micro-electrolysis packing, a highly efficient heterogeneous Fenton oxidation occurred.

[0042] Liquid alkali is added to the neutralization and degassing tank. The liquid alkali added in the neutralization and degassing tank is sodium hydroxide with a mass concentration of 30%. The pH value is adjusted to neutral or slightly alkaline to terminate Fenton oxidation and promote the precipitation of dissolved iron and the removal of gaseous products.

[0043] Adding flocculants (such as PAM) to the flocculation tank causes the iron sludge and suspended solids to coagulate into large flocs, achieving efficient solid-liquid separation and ultimately producing clear and transparent effluent.

[0044] Example 2 A highly efficient multiphase Fenton catalytic reaction system for quartz-recalcitrant wastewater includes, in sequence along the wastewater treatment direction, an inlet tank, a series of multi-stage catalytic reduction towers, a multiphase Fenton catalytic oxidation tank, a neutralization and degassing tank, a flocculation tank, and an inclined plate sedimentation tank. Both the multi-stage catalytic reduction tower and the multiphase Fenton catalytic oxidation tank are filled with micro-electrolysis packing material at the bottom.

[0045] The multi-stage catalytic reduction tower and the multiphase Fenton catalytic oxidation tank are equipped with aeration pipes at the bottom, which are connected to the aeration pipes via an aeration pump to provide air to the catalytic reduction tower. An acid-adjusting tank is located next to the inlet tank to receive and temporarily store wastewater, and acid is added to the wastewater to precisely adjust the pH value to a strongly acidic range of 2.5-2.6, creating the optimal reaction environment for subsequent multiphase catalytic reactions.

[0046] The bottom of the catalytic reduction tower is equipped with micro-electrolysis packing for composite catalysis. This allows for efficient catalytic reduction and ring-opening chain-breaking reactions of stable pollutants in wastewater, such as multi-bonded, high-carbon skeletons, nitro groups, and azo compounds, thereby disrupting their complex structures and reducing the energy barrier for subsequent oxidation reactions.

[0047] The micro-electrolysis filler is composed of iron ions, carbon ions, catalyst noble metal ions, and surfactants, with a particle size of 2-3 cm. The carbon ions in the micro-electrolysis filler are mainly graphene. The surfactants are sodium tripolyphosphate, sodium dodecylbenzenesulfonate, and N,N-dimethylformate in a mass ratio of 5:11:3.

[0048] Fenton reagent (hydrogen peroxide and ferrous sulfate) was added to the Fenton oxidation tank. The mass concentration of hydrogen peroxide added to the Fenton oxidation tank was 27.5%, and the mass concentration of ferrous sulfate was 10%. Under the catalytic action of the micro-electrolysis packing, a highly efficient heterogeneous Fenton oxidation occurred.

[0049] Liquid alkali is added to the neutralization and degassing tank. The liquid alkali added in the neutralization and degassing tank is sodium hydroxide with a mass concentration of 30%. The pH value is adjusted to neutral or slightly alkaline to terminate Fenton oxidation and promote the precipitation of dissolved iron and the removal of gaseous products.

[0050] Adding flocculants (such as PAM) to the flocculation tank causes the iron sludge and suspended solids to coagulate into large flocs, achieving efficient solid-liquid separation and ultimately producing clear and transparent effluent.

[0051] Example 3 A high-efficiency multiphase Fenton catalytic reaction system based on quartz recalcitrant wastewater, the system comprising, in sequence along the wastewater treatment direction, an inlet tank, a multiphase Fenton catalytic oxidation tank, a neutralization and degassing tank, a flocculation tank and an inclined plate sedimentation tank; An acid-adjusting tank is installed next to the inlet tank to receive and temporarily store wastewater, and acid is added to the wastewater to precisely adjust the pH value of the wastewater to a strongly acidic range of 2.5~2.6, creating the best reaction environment for subsequent multiphase catalytic reactions.

[0052] Fenton reagents (hydrogen peroxide and ferrous sulfate) were added to a heterogeneous Fenton catalytic oxidation tank. The mass concentration of hydrogen peroxide added to the Fenton oxidation tank was 27.5%, and the mass concentration of ferrous sulfate was 10%. Under the catalytic action of micro-electrolysis packing and electrode plates, highly efficient heterogeneous Fenton oxidation occurred.

[0053] An alkaline solution is added to the neutralization and degassing tank. The liquid alkali added in the neutralization and degassing tank is sodium hydroxide with a mass concentration of 30%. The pH value is adjusted to neutral or slightly alkaline to terminate Fenton oxidation and promote the precipitation of dissolved iron and the removal of gaseous products.

[0054] Adding flocculants (such as PAM) to the flocculation tank causes the iron sludge and suspended solids to coagulate into large flocs, achieving efficient solid-liquid separation and ultimately producing clear and transparent effluent.

[0055] Application Example 1: Single-stage catalytic reduction mode The wastewater being treated was simulated wastewater prepared by a quartz company. The recalcitrant organic matter in this wastewater was generally difficult for microorganisms to utilize, and conventional biological treatment methods could not meet the treatment standards. The system described in Example 1 was used to treat the wastewater. The operational results were as follows: influent flow rate was 300 L / h; after pretreatment, the pH value was adjusted to between 2.5 and 2.6; hydrogen peroxide dosage was 0.33 mL / L; ferrous sulfate (based on solids) dosage was 0.33 g / L; the reagent ratio was hydrogen peroxide (27.5%): ferrous sulfate (based on solids) = 1:1; and PAM dosage was 1.5 ppm. After multiphase catalytic oxidation, the average COD removal rate of the final effluent from the sedimentation tank was 60-70%.

[0056] Application Example 2: Two-stage catalytic reduction mode The wastewater being treated was simulated wastewater prepared by a quartz company. The recalcitrant organic matter in this wastewater was generally difficult for microorganisms to utilize, and conventional biological treatment methods could not meet the treatment standards. The system described in Example 2 was used to treat the wastewater. The results were as follows: influent flow rate was 300 L / h; after pretreatment, the pH value was adjusted to between 2.5 and 2.6; hydrogen peroxide dosage was 0.33 mL / L; ferrous sulfate (based on solids) dosage was 0.33 g / L; the reagent ratio was hydrogen peroxide (27.5%): ferrous sulfate (based on solids) = 1:1; and PAM dosage was 1.5 ppm. After multiphase catalytic oxidation, the average COD removal rate of the final effluent from the sedimentation tank was 70-80%.

[0057] Application Example 3: Catalytic Reduction Column The wastewater being treated was simulated wastewater prepared by a quartz company. The recalcitrant organic matter in this wastewater was generally difficult for microorganisms to utilize, and conventional biological treatment methods could not meet the treatment standards. The system described in Example 3 was used to treat the wastewater. The operational results were as follows: influent flow rate was 300 L / h; after pretreatment, the pH value was adjusted to between 2.5 and 2.6; hydrogen peroxide dosage was 0.33 mL / L; ferrous sulfate (based on solids) dosage was 0.33 g / L; the reagent ratio was hydrogen peroxide (27.5%): ferrous sulfate (based on solids) = 1:1; and PAM dosage was 1.5 ppm. After multiphase catalytic oxidation, the average COD removal rate of the final effluent from the sedimentation tank was 40-47%.

[0058] The data from Application Examples 1 and 2 show that the average COD removal rate of wastewater from quartz enterprises using either single-stage catalytic reduction combined with a multiphase Fenton catalytic oxidation tank or a multi-stage catalytic reduction combined with a multiphase Fenton catalytic oxidation tank is higher than 60%. Application Example 3, using only a multiphase Fenton catalytic oxidation tank, shows an average COD removal rate below 47%. These results demonstrate that catalytic reduction combined with a multiphase Fenton catalytic oxidation tank can improve the average COD removal rate from wastewater.

[0059] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A highly efficient heterogeneous Fenton catalytic reaction system for recalcitrant quartz wastewater, characterized in that, The system, along the wastewater treatment direction, includes, in sequence, an inlet tank, a catalytic reduction tower, a multiphase Fenton catalytic oxidation tank, a neutralization and degassing tank, a flocculation tank, and an inclined plate sedimentation tank; Both the catalytic reduction tower and the multiphase Fenton catalytic oxidation tank are filled with micro-electrolysis packing at the bottom. The bottom of the catalytic reduction tower and the multiphase Fenton catalytic oxidation tank are equipped with aeration pipes, which are connected to the aeration pipes by an aeration pump to provide gas to the catalytic reduction tower and the multiphase Fenton catalytic oxidation tank.

2. The high-efficiency heterogeneous Fenton catalytic reaction system based on quartz-recalcitrant wastewater according to claim 1, characterized in that, The catalytic reduction tower is composed of a single-stage reduction tower or multiple-stage reduction towers connected in series.

3. The high-efficiency multiphase Fenton catalytic reaction system based on quartz recalcitrant wastewater according to claim 2, wherein the micro-electrolysis packing comprises iron, carbon, noble metal catalysts and surface activators.

4. The efficient multiphase Fenton catalytic reaction system based on quartz recalcitrant wastewater according to claim 2, wherein the surface activator is sodium tripolyphosphate, sodium dodecylbenzenesulfonate and N,N-dimethylformate, in a mass ratio of 3-5:10-12:2-3.

5. A method for treating refractory quartz wastewater using the system described in any one of claims 1-4, characterized in that, Includes the following steps: (1) Place the micro-electrolysis packing material at the bottom of the catalytic reduction tower and the multiphase Fenton catalytic oxidation tank; (2) The wastewater is temporarily stored in the inlet tank, and after the pH is adjusted with sulfuric acid, the wastewater is transported to the inlet of the catalytic reduction tower; (3) Aeration is carried out using an aeration pump at the bottom of the catalytic reduction tower; (4) The wastewater after catalytic reduction treatment is then subjected to catalytic oxidation reaction in a multiphase Fenton catalytic oxidation tank; (5) Wastewater treated by the multiphase Fenton catalytic oxidation tank enters the neutralization and degassing tank, and alkali solution is added to adjust the pH to neutral or weakly alkaline. (6) The water treated in the neutralization and degassing tank enters the flocculation tank for further treatment; (7) The effluent treated by the flocculation tank enters the inclined plate sedimentation tank, and water samples are collected from the outlet of the inclined plate sedimentation tank for analysis and testing.

6. The method according to claim 5, characterized in that, In step (2), adjust the pH to 2.5-2.

6.

7. The method according to claim 5, characterized in that, The micro-electrolysis filler includes iron, carbon, noble metal catalysts and surface activators, with a particle size of 2-3 cm.

8. The method according to claim 5, characterized in that, Hydrogen peroxide and ferrous sulfate are added to the multiphase Fenton catalytic oxidation tank, wherein the mass concentration of hydrogen peroxide is 27.5% and the mass concentration of ferrous sulfate is 10%; the alkaline solution added to the neutralization and degassing tank is sodium hydroxide with a mass concentration of 30%.

9. The method according to claim 7, characterized in that, The carbon is graphene or coke.

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