Carbon-based catalyst packed column in-situ continuous catalysis-regeneration operation method and device

Abstract

The invention particularly relates to an in-situ continuous catalysis-regeneration operation method and device for a carbon-based catalyst packed column. The device comprises a wastewater mixing tank, a catalyst packed column, a clear water storage tank, a power supply and a regenerated liquid storage tank (Figure 1). The method has the beneficial effects that the invention provides the method for in-situ recovery of the catalytic performance of the carbon-based catalyst in the Fenton-like reaction; the carbon-based catalyst activates oxidizing agents such as persulfate, percarbonate and peracetic acid, organic pollutants in water are removed, and after treatment for a period of time, organic products covering active sites of the catalyst are desorbed and decomposed into small-molecule organic products under the combined action of cathode current and oxidizing active species until mineralization is achieved. And the structure of the catalyst is not damaged. And finally, by constructing an in-situ catalytic regeneration cycle operation system, the use amount of the catalyst is saved, continuous water treatment is realized, the operation complexity is reduced, the efficiency is improved finally, and the cost is saved.

Description

Technical Field

[0001] This invention belongs to the field of industrial organic wastewater treatment and sustainable application technology of green materials, and particularly relates to a method and apparatus for in-situ continuous catalytic-regeneration operation of a carbon-based catalyst packing column. Background Technology

[0002] With the advancement of industrialization and the improvement of living standards, industries such as chemicals, pharmaceuticals, and plastics are constantly expanding, releasing new pollutants, including endocrine disruptors, antibiotics, and persistent organic pollutants, into the aquatic environment, causing continuous damage to ecosystems and human health. Carbon-based catalysts, due to their low manufacturing cost and excellent environmental compatibility, have become the preferred choice for heterogeneous advanced oxidation technologies (AOPs) to remove new pollutants. However, in practical applications, organic matter removed through oxidative coupling and polymerization pathways on the catalyst surface can transform into higher molecular weight polymers, which are tightly adsorbed onto the catalyst surface, masking catalytic active sites, leading to catalyst deactivation, significantly shortening catalyst life, and increasing operating costs.

[0003] Among existing technologies for catalyst deactivation, organic solvent cleaning can partially restore catalyst activity; however, chemical reagent cleaning can cause secondary pollution, generate difficult-to-treat organic waste liquid, and has poor activity recovery. Thermal regeneration has high regeneration efficiency and a wide range of applications, but it suffers from problems such as the inability to operate in situ, high energy consumption, and high investment and operating costs.

[0004] Therefore, in order to address the above problems, this invention proposes an in-situ continuous catalytic regeneration operation method and apparatus for carbon-based catalyst packing columns. Through in-situ electrochemical treatment, the polymers attached to the catalyst surface are desorbed and decomposed into small molecule organic products until mineralization, thereby restoring the catalyst activity, significantly extending the catalyst life, and realizing continuous operation of heterogeneous catalytic wastewater treatment. Summary of the Invention

[0005] The purpose of this invention is to provide a method and apparatus for in-situ continuous catalytic regeneration operation of a carbon-based catalyst packed column.

[0006] The technical solution provided by this invention is as follows: This invention provides an in-situ continuous catalytic regeneration operation device for a carbon-based catalyst packing column, comprising a wastewater mixing tank, a catalyst packing column, a clean water storage tank, a regenerated liquid storage tank, and a power supply; the wastewater mixing tank is connected to the lower treated water inlet of the catalyst packing column via an inlet valve; the clean water storage tank is connected to the upper treated water outlet of the catalyst packing column via an outlet valve; the lower outlet of the regenerated liquid storage tank is connected to the lower regenerated liquid inlet of the catalyst packing column via an inlet valve, and the upper inlet of the regenerated liquid storage tank is connected to the upper regenerated liquid outlet of the catalyst packing column via an outlet valve; the power supply for providing current during the regeneration stage is connected to the upper anode of the catalyst packing column via an anode wire and to the lower cathode of the catalyst packing column via a cathode wire.

[0007] In this invention, the catalyst packing column is mainly divided into three parts: the catalyst layer is located in the middle of the column and is fixed by supporting materials above and below; the anode is located in the upper part of the column; and the cathode extends from the lower part of the column through the entire catalyst layer to cathodize the catalyst. The catalytic operation and regeneration operation are both carried out in situ, and there is no need to load, unload, or transport the catalyst layer.

[0008] Preferably, the supporting material for fixing the catalyst layer is selected from nano sponges, porous water distribution plates, stainless steel filter plates, porous titanium plates, and other materials that allow water to pass through but can retain the catalyst, and whose pore size is smaller than the particle size of the catalyst packing.

[0009] More preferably, the conductive materials used for the anode and cathode are selected based on resistance requirements and economic budget, such as silver, copper, titanium, graphite, carbon fiber, cupronickel alloy, stainless steel, and titanium alloy; the electrode shapes for the anode and cathode are selected based on the form of the filler column, including wire rod, annular disc, and mesh.

[0010] In this invention, the carbon-based catalyst used has good catalytic and electrical conductivity properties, and the selected materials include carbon nanotubes, modified carbon nanotubes, graphene, graphite, and biochar.

[0011] In this invention, persulfate is added to the organic wastewater in a wastewater mixing tank and mixed evenly.

[0012] Preferably, the concentration range of persulfate added is 0.2 to 100 mM, and the amount added depends on the concentration and type of pollutant.

[0013] In this invention, the regenerated liquid in the regenerated liquid storage tank consists of electrolytes and oxidants of a certain concentration.

[0014] Preferably, the electrolyte is selected according to the application scenario and includes sodium sulfate, borate buffer, phosphate buffer, and potassium hydroxide; the oxidant is selected according to the application scenario and includes products that are easily activated at the cathode to generate oxidative active species, such as hydrogen peroxide, peracetic acid, percarbonate, and hydroxylamine; the electrolyte concentration range is 5 to 300 mM, and the oxidant concentration range is 5 to 30 mM.

[0015] In this invention, during regeneration, the power supply mode is selected as either constant current mode or constant voltage mode.

[0016] Preferably, the current range and voltage range are determined according to the amount of filler and the size of the device; the current range is between 0.1 and 20A, the voltage range is between 0.5 and 20V, and the energizing time is selected within 0.5 to 5 hours according to the regeneration effect.

[0017] The present invention also provides a method for in-situ continuous catalytic regeneration operation of a carbon-based catalyst packing column based on the above-mentioned device, which is carried out according to the following steps: S1. Open the treated water inlet valve (6) and the treated water outlet valve (7), and close the regenerated liquid inlet valve (8) and the regenerated liquid outlet valve (9). The wastewater is first mixed evenly with persulfate in the mixing tank (1). The mixed wastewater is pumped from the bottom of the catalyst packing column (2) by a peristaltic pump, flows upward through the catalyst, and is discharged from the top outlet and collected in the clear water tank (3). S2. After the set wastewater treatment time is reached, close the treated water inlet valve (6) and the treated water outlet valve (7), open the regenerated liquid inlet valve (8) and the regenerated liquid outlet valve (9), pump the regenerated liquid into the catalyst packing column (2) from the bottom through the peristaltic pump, and after the regenerated liquid fills the column, connect the power supply (5) to power on for the set time, turn off the power supply, and return the regenerated liquid to the regenerated liquid storage tank (4). S3. Re-pump the mixed wastewater for treatment and repeat the above operation steps.

[0018] The beneficial effects of this invention are: In practical applications of heterogeneous Fenton-like advanced oxidation technologies based on carbon-based catalysts, high-molecular-weight polymers and various reaction intermediates are generated via electron transfer pathways. These products complex with active sites and adhere tightly to the catalyst surface due to hydrophobic interactions, leading to catalyst deactivation. This invention proposes an in-situ continuous catalytic regeneration method and apparatus for carbon-based catalyst packed columns. After continuous use until deactivation, the catalyst undergoes in-situ electrochemical regeneration to adjust the hydrophilicity / hydrophobicity and surface charge of the catalyst surface, helping catalytic products detach from the catalyst surface and re-expose catalytic active sites. Furthermore, an appropriate amount of oxidant is introduced to induce an electro-Fenton reaction during regeneration, generating oxidizing active species that deeply clean the organic matter adhering to the catalyst surface, efficiently restoring its catalytic activity. This significantly extends catalyst life and reduces industrial production costs. Attached Figure Description

[0019] Figure 1 This is a schematic diagram of the structure of the in-situ continuous catalytic regeneration operation device for the carbon-based catalyst packing column of the present invention.

[0020] Figure 2 The image shows the effect of the catalyst-packed column on the treatment of phenol wastewater in Example 2.

[0021] Figure 3 The image shows the treatment effect of the catalyst-packed column on different organic wastewaters in Example 3.

[0022] Figure 4 The graph shows the change in persulfate utilization rate during the catalytic treatment process in Example 4.

[0023] Figure 5 This is a comparison chart of the treatment effects of the catalyst used and the original catalyst on phenol wastewater in Example 5.

[0024] Figure 6 The image shows the effect of the catalyst on the treatment of phenol wastewater after regenerating the deactivated catalyst using different current magnitudes in Example 6.

[0025] Figure 7 The image shows the effect of the catalyst on the treatment of phenol wastewater after regenerating the deactivated catalyst using different hydrogen peroxide concentrations, as shown in Example 7.

[0026] Figure 8 The image shows the effect of the catalyst on the treatment of phenol wastewater after regenerating the deactivated catalyst using different regeneration times in Example 8.

[0027] Figure 9 (a) SEM image of the original NCNT catalyst, (b) SEM image of the NCNT catalyst after deactivation, and (c) SEM image of the NCNT catalyst after regeneration.

[0028] Figure 10 The diagram shows the effect of five cycles of phenol wastewater treatment using the in-situ continuous catalytic regeneration device with carbon-based catalyst packing column in Example 9.

[0029] Figure 11 This is a diagram showing the long-term treatment effect of the carbon-based catalyst packed column in-situ continuous catalytic regeneration device on coking wastewater in Example 10.

[0030] Explanation of reference numerals in the attached figures: 1. Wastewater mixing tank; 2. Catalyst packing column; 3. Clean water storage tank; 4. Regenerated liquid storage tank; 5. Power supply; 6. Treated water inlet valve; 7. Treated water outlet valve; 8. Regenerated liquid inlet valve; 9. Regenerated liquid outlet valve. Detailed Implementation

[0031] The present invention will be further described below with reference to embodiments. The description of the embodiments below is only for the purpose of helping to understand the present invention. It should be noted that those skilled in the art can make several modifications to the present invention without departing from the principle of the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.

[0032] Example 1 Methods for designing small catalyst packed columns for subsequent validation experiments: A small packed column with an inner diameter of 8 mm and a height of 100 mm was filled with 100 mg of catalyst. The column mainly consists of three parts: a catalytic packing layer with a height of 20 mm, an anode, and a cathode. A 10 mm high nanofiber sponge block was placed at each end of the catalytic packing layer as a support layer. Pure titanium wire was selected as both the anode and cathode; the cathode titanium wire passed through the catalytic packing layer to cathodically polarize the catalyst during electroregeneration. The electrode spacing between the anode and cathode was maintained at 10 mm.

[0033] The specific layout of the reaction apparatus is shown in the schematic diagram. Figure 1 As shown in the figure.

[0034] Example 2 Methods for catalytic treatment of phenol wastewater: According to Example 1, a catalyst-packed column was assembled to prepare a phenol wastewater mixture: 0.5 ml of a 100 mM persulfate solution (PMS) was added to 499.5 ml of a 0.1 mM phenol (PE) solution, and the mixture was stirred thoroughly. The mixture was then passed into the packed column for treatment with a hydraulic residence time of 2 min in the catalyst layer. Samples were taken at the outlet of the packed column. Sampling times were 0, 30, 60, 90, 120, 180, 240, and 300 minutes. The concentration of pollutants in the samples was analyzed using liquid chromatography to determine the removal efficiency. The treatment effect ( Figure 2 It can be seen that the present invention can efficiently remove phenol.

[0035] Example 3 Methods for catalytic treatment of different organic wastewaters (bisphenol A (BPA), o-chlorophenol (COP), p-chloro-m-cresol (PCMX), dimethylphenol (DMP), sulfamethoxazole (SMX), sulfapyridine (SPY), sulfathiazole (STZ), sulfadiazine (SMM)): Prepare mixed solutions of different organic wastewaters: Add 0.5 ml of 100 mM persulfate (PMS) solution to 499.5 ml of 0.1 mM organic pollutant solution and stir thoroughly. Pass the mixture into a packed column for treatment with a hydraulic residence time of 2 min in the catalyst bed, and take samples at the outlet of the packed column. Sampling times are 0, 30, 60, 90, 120, 180, 240, and 300 minutes. Analyze the concentration of pollutants in the samples using liquid chromatography to determine the removal efficiency. The treatment effect ( Figure 3 It can be seen that the present invention can efficiently remove a variety of organic pollutants.

[0036] Example 4 Methods for detecting changes in persulfate (PMS) utilization during catalytic treatment: The sample collection method was the same as in Example 2. The concentration of permonosulfate (PMS) in the sample was determined by iodometric titration: 0.5 ml of 0.1 M potassium hydrogen phthalate solution, 0.5 ml of 0.4 M potassium iodide solution, and 20 μL of sample were added to 0.98 ml of pure water, mixed thoroughly, allowed to stand for 30 min for color development, and then the absorbance was measured at 350 nm to determine the permonosulfate (PMS) utilization rate. The change in the utilization rate of the oxidant (…) Figure 4 As can be seen, the utilization rate of the oxidant gradually decreases as the reaction time progresses, which corresponds to the gradual deactivation of the catalyst.

[0037] Example 5 Methods that lead to decreased activity when using catalyst packed columns: According to Example 2, after catalytic treatment of phenol wastewater using a catalyst-packed column for 300 min, the mixture was further passed into the packed column for treatment with a hydraulic residence time of 2 min in the catalyst layer. Samples were taken at the outlet of the packed column. Sampling times were 0, 30, 60, 90, 120, 180, 240, and 300 minutes. The concentration of pollutants in the samples was analyzed using liquid chromatography to determine the removal efficiency after the catalyst activity decreased.

[0038] The treatment effect compared with the original catalyst shows that ( Figure 5The activity of catalysts will decrease significantly after prolonged use.

[0039] Example 6 Methods for regenerating deactivated catalysts under different current magnitudes: Preparation of regenerated solution: 77 μL of 30% hydrogen peroxide solution was added to 25 mL of 100 mM sodium sulfate solution and mixed thoroughly. Following Example 2, after catalytic treatment of phenol wastewater using a catalyst-packed column for 300 min, the regenerated solution was passed into the catalyst-packed column until the column was full. A constant current of 0.3 mA was applied to the catalyst layer for 30 min. After the set time was reached, the regenerated solution was discharged, and then pure water was passed through at a flow rate of 1 mL / min to wash away any remaining regenerated solution in the column. Example 2 was repeated, and the removal efficiency after regeneration was measured. Following Example 2, after catalytic treatment of phenol wastewater using a catalyst-packed column for 300 min, the regenerated solution was passed into the catalyst-packed column until the column was full. A constant current of 0.5 mA was applied to the catalyst layer for 30 min. After the set time was reached, the regenerated solution was discharged, and then pure water was passed through at a flow rate of 1 mL / min to wash away any remaining regenerated solution in the column. Example 2 was repeated, and the removal efficiency after regeneration was measured. Following Example 2, after catalytic treatment of phenol wastewater using a catalyst-packed column for 300 min, the regenerated liquid was passed into the catalyst-packed column until the column was full. A constant current of 1 mA was applied to the catalyst layer for 30 min. After the set time was reached, the regenerated liquid was discharged, and then pure water was passed through at a flow rate of 1 ml / min to wash away any remaining regenerated liquid in the packing column. Example 2 was repeated, and the removal efficiency after regeneration was measured. Following Example 2, after catalytic treatment of phenol wastewater using a catalyst-packed column for 300 min, the regenerated liquid was passed into the catalyst-packed column until the column was full. A constant current of 1.5 mA was applied to the catalyst layer for 30 min. After the set time was reached, the regenerated liquid was discharged, and then pure water was passed through at a flow rate of 1 ml / min to wash away any remaining regenerated liquid in the packing column. Example 2 was repeated, and the removal efficiency after regeneration was measured. The treatment effect (regeneration effect) of the catalyst after regeneration treatment of the deactivated catalyst at different current magnitudes is as follows: Figure 6 As shown.

[0040] Example 7 Methods for regenerating deactivated catalysts at different hydrogen peroxide concentrations: This embodiment is basically the same as embodiment 6, except that: Following Example 2, phenol wastewater was catalytically treated with a catalyst-packed column for 300 min. Then, regeneration was performed by applying a constant current of 1 mA to the catalyst layer for 30 min using regeneration solutions with different hydrogen peroxide concentrations. The treatment effect of the catalyst on phenol wastewater was then measured.

[0041] Prepare regenerated solutions with different peroxide concentrations: 1) Take 0 μL of 30% hydrogen peroxide solution and add it to 25 mL of 100 mM sodium sulfate solution. Mix well to prepare a regeneration solution with a hydrogen peroxide concentration of 0 mM.

[0042] 2) Take 26 μL of 30% hydrogen peroxide solution and add it to 25 mL of 100 mM sodium sulfate solution. Mix well to prepare a regeneration solution with a hydrogen peroxide concentration of 10 mM.

[0043] 3) Take 77 μL of 30% hydrogen peroxide solution and add it to 25 mL of 100 mM sodium sulfate solution. Mix well to prepare a regeneration solution with a hydrogen peroxide concentration of 30 mM.

[0044] 4) Take 129 μL of 30% hydrogen peroxide solution and add it to 25 mL of 100 mM sodium sulfate solution. Mix well to prepare a regeneration solution with a hydrogen peroxide concentration of 50 mM.

[0045] The regeneration effect of the deactivated catalyst after regeneration treatment at different hydrogen peroxide concentrations is as follows: Figure 7 As shown.

[0046] Example 8 Methods for regenerating deactivated catalysts at different regeneration times: This embodiment is basically the same as embodiment 6, except that: Following Example 2, after catalytic treatment of phenol wastewater with a catalyst-packed column for 300 min, a regenerated solution with a hydrogen peroxide concentration of 30 mM was passed into the catalyst-packed column until the column was filled. A constant current of 1 mA was applied to the catalyst layer for different times (15 min, 30 min, 45 min, 60 min) for regeneration treatment. The treatment effect of the catalyst on phenol wastewater was then measured.

[0047] The regeneration effect of the deactivated catalyst after regeneration treatment at different regeneration times is as follows: Figure 8 As shown.

[0048] The removal effects of the deactivated catalysts obtained in Examples 5 to 8 after 300 minutes of operation without regeneration and after regeneration are shown in Table 1 below: Table 1. Comparison of phenol removal efficiency of deactivated catalysts in Examples 5-8 after 300 min of operation with and without regeneration.

[0049] Note: Regeneration rate (%) = Removal rate of catalyst after regeneration (%) after 300 min of use / Removal rate of original catalyst after 300 min of use (%) As can be seen from the results in Table 1 above, the in-situ electrochemical regeneration method developed by this invention for the deactivation of carbon-based catalysts in Fenton-like reactions can flexibly adjust various key parameters and select the optimal parameters to achieve ideal regeneration results. It can be flexibly adjusted according to different application scenarios.

[0050] Example 9 Methods for in-situ continuous catalytic regeneration operation of carbon-based catalyst packed columns: According to Example 2, phenol wastewater was catalytically treated using a catalyst-packed column for 300 min, and the removal efficiency during the treatment process was determined. Preparation of the regenerated solution: 77 μL of 30% hydrogen peroxide solution was added to 25 mL of 100 mM sodium sulfate solution and mixed thoroughly. The regenerated solution was passed into the catalyst-packed column until the column was full. A constant current of 1 mA was applied to the catalyst layer for 60 min. After the set time was reached, the regenerated solution was discharged, and then pure water was passed through at a flow rate of 1 mL / min to wash away any remaining regenerated solution in the packed column. The above three steps were repeated for five cycles. SEM images of the catalyst before and after regeneration were used. Figure 9 ) and the effect of 5 treatments ( Figure 10 As can be seen, the regeneration process can efficiently maintain the catalyst activity without significantly affecting the catalyst's structure, demonstrating the good stability of this invention.

[0051] Example 10 Methods for treating coking wastewater using in-situ continuous catalytic regeneration operation of carbon-based catalyst packed columns: Four catalyst packing columns were assembled according to Example 1 and connected in series with water pipes. Coking wastewater was passed into the packing columns for treatment with a hydraulic residence time of 2 min per catalyst layer, and samples were taken at the outlet of the packing columns. Sampling times were 0, 2, 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, and 30 hours. The total organic carbon concentration in the samples was analyzed using a TOC analyzer to determine the removal efficiency. Preparation of the regenerant: 309 μL of 30% hydrogen peroxide solution was added to 100 mL of 100 mM sodium sulfate solution and mixed thoroughly. The regenerant was passed into each catalyst packing column until the column was full. A constant current of 1 mA was applied to the catalyst layer for 120 min. After the set time was reached, the regenerant was discharged, and then pure water was passed through at a flow rate of 1 mL / min to wash away any remaining regenerant in the packing columns. Step 2 was repeated, with sampling time of 20 hours, to determine the removal efficiency of the regenerated device for coking wastewater. Processing results ( Figure 11 As can be seen, multi-stage series carbon-based catalyst packing columns can effectively treat coking wastewater within a certain period of time, and can efficiently restore catalytic activity after regeneration, thus possessing industrial application potential.

Claims

1. A carbon-based catalyst packed column in-situ continuous catalytic regeneration operation device, characterized in that, It includes a wastewater mixing tank (1), a catalyst packing column (2), a clean water storage tank (3), a regenerated liquid storage tank (4), and a power supply (5); the wastewater mixing tank (1) is connected to the lower part of the catalyst packing column (2) via a treated water inlet valve (6); the clean water storage tank is connected to the upper part of the catalyst packing column via a treated water outlet valve (7); the lower part of the regenerated liquid storage tank (4) is connected to the lower part of the catalyst packing column (2) via a regenerated liquid inlet valve (8), and the upper part of the regenerated liquid storage tank (4) is connected to the upper part of the catalyst packing column (2) via a regenerated liquid outlet valve (9); the power supply (5) used to provide current in the regeneration stage is connected to the upper anode of the catalyst packing column (2) via an anode wire and to the lower cathode of the catalyst packing column (2) via a cathode wire.

2. The in-situ continuous catalytic regeneration operation device for carbon-based catalyst packed columns according to claim 1, characterized in that, The catalyst packing column (2) is mainly divided into three parts: the catalyst layer is located in the middle of the column and is fixed by supporting materials above and below; the anode is located in the upper part of the column; the cathode extends from the lower part of the column to the entire catalyst layer to make the catalyst cathodic; the catalytic operation and regeneration operation are carried out in situ.

3. The in-situ continuous catalytic regeneration operation device for carbon-based catalyst packed columns according to claim 1, characterized in that, In the catalyst packing column (2), the supporting material for fixing the catalyst layer is selected from nano sponge, porous water distribution plate, stainless steel filter plate, porous titanium plate and other porous support materials. Its pore size is smaller than the particle size of the catalyst, which is easy to pass water through but can retain the catalyst.

4. The in-situ continuous catalytic regeneration operation device for carbon-based catalyst packed column according to claim 1, characterized in that, In the catalyst packing column (2), the conductive materials selected for the anode and cathode ends are chosen according to the resistance requirements, including silver, copper, titanium, graphite, carbon fiber, cupronickel alloy, stainless steel, and titanium alloy; the electrode shapes of the anode and cathode ends include wire rod, ring disk, mesh, and block.

5. The in-situ continuous catalytic regeneration operation device for carbon-based catalyst packed columns according to claim 1, characterized in that, The carbon-based catalysts used have good catalytic and electrical conductivity properties, and the selected catalysts are carbon nanotubes, modified carbon nanotubes, graphene, graphite, and biochar.

6. The in-situ continuous catalytic regeneration operation device for carbon-based catalyst packed column according to claim 1, characterized in that, In the wastewater mixing tank (1), persulfate is added to the organic wastewater at a concentration range of 0.2 to 100 mM. The amount added depends on the concentration and type of pollutants. The mixture is then thoroughly mixed.

7. The in-situ continuous catalytic regeneration operation device for carbon-based catalyst packed columns according to claim 1, characterized in that, In the regenerated liquid storage tank (4), the regenerated liquid is composed of electrolyte and oxidant solutions of a certain concentration; the electrolyte is selected according to the application scenario and includes sodium sulfate, borate buffer, phosphate buffer and potassium hydroxide; the oxidant is selected according to the application scenario and is a product that is easily activated at the cathode to generate oxidative active species, such as hydrogen peroxide, peracetic acid, percarbonate and hydroxylamine; the electrolyte concentration range is 5 to 300 mM and the oxidant concentration range is 5 to 30 mM.

8. The in-situ continuous catalytic regeneration operation device for carbon-based catalyst packed column according to claim 1, characterized in that, During regeneration, select either constant current mode or constant voltage mode. The current and voltage ranges are determined based on the amount of packing material and the size of the device. The current range is 0.1~20 A, and the voltage range is 0.5~20 V. The energizing time is selected from 0.5 to 5 hours based on the regeneration effect.

9. The in-situ continuous catalytic regeneration operation device for carbon-based catalyst packed columns according to claim 1, characterized in that, include: S1. Open the treated water inlet valve (6) and the treated water outlet valve (7), and close the regenerated liquid inlet valve (8) and the regenerated liquid outlet valve (9). The wastewater is first mixed evenly with persulfate in the mixing tank (1). The mixed wastewater is pumped from the bottom of the catalyst packing column (2) by a peristaltic pump, flows upward through the catalyst, and is discharged from the top outlet and collected in the clear water tank (3). S2. After the set wastewater treatment time is reached, close the treated water inlet valve (6) and the treated water outlet valve (7), open the regenerated liquid inlet valve (8) and the regenerated liquid outlet valve (9), pump the regenerated liquid into the catalyst packing column (2) from the bottom through the peristaltic pump, and after the regenerated liquid fills the column, connect the power supply (5) to power on for the set time, turn off the power supply, and return the regenerated liquid to the regenerated liquid storage tank (4). S3. Re-pump the mixed wastewater for treatment and repeat the above operation steps.

Images