Method for preparing sulfur-doped bone black catalyst and method for treating coking wastewater

Abstract

The invention belongs to the technical field of coking wastewater treatment, and particularly relates to a method for preparing a sulfur-doped bone black catalyst and treating coking wastewater, sulfur-doped bone black is bone black doped with sulfur element, and the method comprises the following steps: preparing bone meal slurry: performing high-temperature treatment, crushing and grinding on animal bones to obtain bone meal; bone meal and a solvent are mixed, and bone meal slurry is obtained; 2) preparing bone black precursor powder: adding a sulfur-containing substance into the bone powder slurry, and stirring at a constant temperature; 3) bone pre-carbonization: carrying out high-temperature pre-reaction, alcohol washing and drying on the bone black precursor; and 4) preparing sulfur-doped bone black: grinding the pre-carbonized bone black, calcining in an inert atmosphere, grinding, pickling, washing with alcohol, and drying. The preparation method has the advantages that the framework structure of the bovine bone black can be remarkably improved by sulfur doping, so that the sulfur-doped bone black has higher specific surface area and porosity, and shows an adsorption effect on nonbiodegradable organic matters in coking wastewater superior to that of other bone black.

Description

Technical Field

[0001] The present invention belongs to the technical field of coking wastewater treatment, and particularly relates to a method for preparing a sulfur-doped bone char catalyst and treating coking wastewater. Background Art

[0002] Coke, as a representative product of the traditional coal chemical industry, plays an important role in the steel industry. However, as a highly polluting and water-consuming industry, a large amount of wastewater is generated in each process of coal coking. Therefore, coking wastewater has a large production volume, high pollutant concentration, and high treatment difficulty, and is recognized as difficult-to-treat industrial wastewater. The composition of coking wastewater is complex, and its organic components are mainly phenolic compounds, nitrogen-containing heterocyclic compounds, and polycyclic aromatic hydrocarbons. In addition, coking wastewater also contains inorganic pollutants such as ammonia, cyanide, and thiocyanate, as well as heavy metals. It is difficult to meet the standards for coking wastewater treated by conventional biological treatment methods, and there are still pollutants that are difficult to biodegrade, such as polycyclic aromatic hydrocarbons, alkylphenols, and amines, in the biochemical effluent, and the biochemical wastewater needs to be deeply treated. It is very necessary to develop an efficient, green, universal, and low-cost coking wastewater deep treatment technology.

[0003] Advanced oxidation processes (AOPs) can generate active species to in-situ degrade and mineralize organic matter, and are one of the effective means to decompose organic micropollutants. Common oxidants include hydrogen peroxide (H2O2), persulfate (PDDS), and peroxymonosulfate (PMS), etc. In recent years, peracetic acid (PAA) has also been applied in the purification of sewage by advanced oxidation processes as an efficient and economical oxidant. PAA has a relatively high redox potential (1.06 - 1.96 eV). It has a similar O - O bond to persulfate and hydrogen peroxide, but its bond dissociation energy is lower than that of other oxidants. Therefore, it can generate a variety of free radicals, including hydroxyl radicals and organic radicals. Lower toxicity and higher selectivity make peracetic acid a new advanced oxidation system with great development potential. The advanced oxidation technology based on PAA has the characteristic of high synchronous disinfection ability while degrading organic pollutants, and PAA has certain advantages in the treatment of medical wastewater. In the prior art, patent publication number: CN117776371A, discloses a method for treating medical wastewater by activating peracetic acid with iron-nitrogen co-doped biochar, using iron-nitrogen co-doped biochar as the material for activating peracetic acid, but the material synthesis process is relatively cumbersome, requires the addition of an additional reducing agent, and directly adds peracetic acid to complete the reaction. Patent publication number: CN117619365A, discloses a supported iron biochar and its preparation method and application, using straw as the biochar raw material and hydrates of ferric chloride, ferric sulfate, and ferric nitrate as the iron source, and obtaining supported iron biochar by one-step high-temperature calcination. It can effectively improve the treatment efficiency of sulfonamide antibiotic wastewater, but this invention needs to directly add peracetic acid to complete the reaction, and at the same time, the catalyst contains iron elements, there is a risk of secondary pollution.

[0004] The activation pathways of PAA mainly include activation through external energy input (e.g., thermal activation, ultraviolet activation, photocatalysis, etc.) and activation through homogeneous / heterogeneous catalysts. Since the cost of activation methods using high-energy input such as ultraviolet light is relatively high, relatively speaking, activating PAA with catalysts is more economically viable. Among them, heterogeneous metal-based catalysts have attracted extensive attention due to their high catalytic activity, convenient recycling, and less influence by water quality.

[0005] Although peracetic acid is a promising oxidant, it is limited due to its strong pungent odor, high volatility, easy explosion at low temperatures and concentrations exceeding 45%, instability, difficulty in transportation, and the need for continuous titration to determine its concentration. Therefore, there is an urgent need for a new activation method to solve this problem. Utilizing solid oxygen-based activators and peroxides to in-situ generate peracetic acid and then using a catalyst for activation to achieve pollutant degradation not only avoids the risks of directly adding peracetic acid but also has the characteristics of safe and convenient operation, higher utilization efficiency of peracetic acid, strong stability, a wide pH application range, and can avoid acidification of the effluent, showing great application potential. Summary of the Invention

[0006] To overcome the deficiencies of the prior art, the purpose of the present invention is to provide a method for preparing a sulfur-doped bone char catalyst and treating coking wastewater, which uses sulfur-doped bone char to activate peracetic acid to economically and efficiently treat coking wastewater and solve the problems of difficult degradation and difficult treatment of organic matter in the existing coking wastewater treatment process.

[0007] To achieve the above purpose, the present invention is realized through the following technical solutions:

[0008] A method for preparing a sulfur-doped bone char catalyst, wherein the sulfur-doped bone char is bone char doped with sulfur elements; the preparation process includes the following steps:

[0009] 1) Prepare bone powder slurry: Perform high-temperature treatment, crushing, and grinding on animal bones to obtain bone powder; mix the bone powder with a solvent, stir, and ultrasonicate to obtain bone powder slurry;

[0010] 2) Prepare bone char precursor powder: Add a sulfur-containing substance to the bone powder slurry obtained in step 1), stir at a constant temperature to obtain a bone char precursor;

[0011] 3) Pre-carbonize the bone: Perform a high-temperature pre-reaction on the bone char precursor obtained in step 2), wash with alcohol, and dry to obtain pre-carbonized bone char;

[0012] 4) Prepare sulfur-doped bone char: Grind the pre-carbonized bone char obtained in step 3), calcine it in an inert atmosphere, grind it, wash it with acid, wash it with alcohol, and dry it to obtain sulfur-doped bone char.

[0013] The phosphorus dry weight content in the animal bone described in step 1) is 17% - 21%.

[0014] The high-temperature treatment described in step 1) is boiling in boiling water for 1 - 3 h; the grinding is ball milling, and the ball milling conditions are: the ball milling speed is 600 - 800 r / min, the ball milling time is 120 - 240 min, and the ball-to-material ratio is 50 - 100:1; the particle size of the bone powder is 0.5 - 2.5 mm;

[0015] The stirring is carried out under the condition of a rotation speed of 600 - 800 r / min; the stirring time is 60 - 90 min; the ultrasonic time is 20 - 30 min.

[0016] In step 1), the bone powder is 3 - 5 g, the solvent is deionized water or ethanol, and the dosage is 50 - 100 ml; in step 2), the sulfur-containing substance is sulfur powder, sodium polysulfide or sulfuric acid, the addition amount of sulfur powder or sodium polysulfide is 0.45 - 1.25 g, the mass concentration of sulfuric acid is 10% - 15%, and the addition amount is 15 - 20 ml.

[0017] The high-temperature pre-reaction described in step 3) is heating in a high-temperature oven, and the heating conditions are: first heating at a temperature of 250 - 300 °C for 3 - 4 h, and then heating at a temperature of 350 - 400 °C for 4 - 6 h; the drying temperature is 60 - 80 °C, and the drying time is 10 - 12 h.

[0018] The calcination under an inert atmosphere described in step 4) is calcination in a tubular furnace under an inert gas atmosphere. The inert gas is nitrogen, argon or helium, the gas flow rate is 0.3 - 0.5 L / min, the calcination temperature is 850 - 950 °C, the heating rate is 5 - 15 °C / min, and the calcination time is 2 - 3 h; the grinding time is 20 - 40 min; the acid used for pickling is glacial acetic acid, hydrochloric acid or sulfuric acid; the drying temperature is 60 - 80 °C, and the drying time is 12 - 20 h.

[0019] The conditions for the constant-temperature stirring described in step 2) are: temperature 60 - 70 °C, stirring speed 1000 - 1200 r / min, and stirring time 120 - 180 min.

[0020] A method for treating coking wastewater with a sulfur-doped bone char catalyst, which uses sulfur-doped bone char to activate peracetic acid to treat the biochemical effluent of coking wastewater. The treatment method of the coking wastewater includes the following steps:

[0021] 1) Prepare a sulfur-doped bone char filter membrane: Dissolve sulfur-doped bone char in an organic solvent, disperse it by ultrasonic wave, vacuum filter the obtained sulfur-doped bone char dispersion liquid onto a filter membrane, wash it with alcohol, and dry it to obtain a sulfur-doped bone char filter membrane;

[0022] 2) Degradation reaction of coking wastewater: Fix the sulfur-modified bovine bone charcoal filter membrane onto the membrane module, and use the coking wastewater added with oxygen-based surfactant and peroxide as the feed liquid to carry out a cyclic catalytic degradation reaction.

[0023] The organic solvent described in step 1) is one of dimethylformamide, N,N-dimethylacetamide, and glycerol;

[0024] In the feed liquid described in step 2), the oxygen-based surfactant is tetraacetylethylenediamine with a concentration of 5 - 10 mM; the peroxide is sodium percarbonate with a concentration of 5 - 10 mM.

[0025] The feed liquid described in step 2) enters the reaction vessel in a top-down manner, and a water circulation is driven by a circulation pump in the reactor. The reaction time is 3 h - 6 h, and the output pressure of the circulation pump is 0.05 - 0.1 bar.

[0026] Compared with the prior art, the beneficial effects of the present invention are:

[0027] 1) In the present invention, sulfur doping can significantly improve the framework structure of bovine bone charcoal, making the sulfur-doped bone charcoal have a higher specific surface area and porosity, and showing a better adsorption effect on the refractory biodegradable organic matter in coking wastewater than other bone charcoals.

[0028] 2) In the present invention, the segmented high-temperature treatment of bone charcoal during the synthesis process of bone charcoal effectively avoids the loss of sulfur components, enabling the doped sulfur to replace the phosphorus originally present in the bone during the reaction to form more active sites, so that the obtained sulfur-doped bone charcoal has specific degradation performance for the refractory cyclic lipid organic matter in coking wastewater.

[0029] 3) Compared with the existing carbon materials, the sulfur-doped bone charcoal has a wide range of material sources, overcomes the secondary pollution problems caused by traditional metal-doped bone charcoal materials, such as iron sludge, high toxicity of cobalt ions, etc. By preparing porous carbon bone charcoal through non-metal doping, the specific surface area of the material can be increased and the number of active sites can be increased. The combination of sulfur-doped bone charcoal and the membrane can activate the in-situ generated peracetic acid, avoiding the safety problems of directly adding peracetic acid and the problem of effluent acidification, and at the same time facilitating the recycling of sulfur-doped bone charcoal. Description of the Drawings

[0030] Figure 1 It is a curve graph of the degradation of coking wastewater COD by sulfur-doped bone charcoal activating peracetic acid in Examples 4 - 6. Detailed Embodiments

[0031] The present invention will be described in detail below with reference to the accompanying drawings of the specification, but it should be noted that the implementation of the present invention is not limited to the following embodiments.

[0032] The materials and instruments used in the following examples are all commercially available, and the raw materials are of analytical purity. In the following examples, unless otherwise specified, the obtained data are the averages of more than three repeated experiments.

[0033] Example 1

[0034] This example provides a preparation method of sulfur-doped bone char, specifically as follows:

[0035] S1. Take animal bones with a phosphorus dry weight content of 18.17% and boil them in boiling water for 1 h, then air-dry them naturally, crush them, place them in a ball mill, and ball mill for 120 min under the conditions of a ball-to-material ratio of 50:1 and a rotation speed of 600 r / min to obtain bone powder with a particle size of 2.5 mm; mix 3 g of the obtained bone powder with 50 ml of deionized water, continuously stir at a rotation speed of 600 r / min for 90 min, and then perform ultrasonic treatment for 20 min to obtain a bone powder slurry. The animal bones can be bovine bones.

[0036] S2. Add 0.45 g of sulfur powder to the bone powder slurry obtained in step S1, and stir at a constant temperature of 60 °C and a rotation speed of 1200 r / min for 180 min to obtain a bone char precursor.

[0037] S3. Transfer the bone char precursor obtained in step S2 to an oven preheated to 300 °C and heat for 3 h. Then raise the temperature of the oven to 400 °C and heat at 400 °C for 4 h, and dry at 60 °C for 12 h to obtain pre-carbonized bone char.

[0038] S4. After grinding the pre-carbonized bone char obtained in step S3 for 20 min, transfer the pre-carbonized bone char to a crucible and place it in a tube furnace. Under a nitrogen atmosphere with a gas flow rate of 0.5 L / min, heat it at a heating rate of 5 °C / min to 850 °C, and calcine at 850 °C for 180 min. After cooling and grinding into components, perform pickling with glacial acetic acid and alcohol washing, and then dry at 60 °C for 20 h to obtain sulfur-doped bone char, denoted as S / BBC850.

[0039] Example 2

[0040] This example provides a preparation method of sulfur-doped bone char, specifically as follows:

[0041] S1. Take animal bones with a phosphorus dry weight content of 19.35% and boil them in boiling water for 2 h, then air-dry them naturally, crush them, place them in a ball mill, and ball mill for 180 min under the conditions of a ball-to-material ratio of 75:1 and a rotation speed of 700 r / min to obtain bone powder with a particle size of 1.5 mm; mix 4 g of the obtained bone powder with 75 ml of deionized water, continuously stir at a rotation speed of 700 r / min for 75 min, and then perform ultrasonic treatment for 25 min to obtain a bone powder slurry.

[0042] S2. Add 15 ml of sulfuric acid with a mass concentration of 10% to the bone meal slurry obtained in step S1, and stir it at a constant temperature of 65 °C and 1100 r / min for 150 min to obtain a bone char precursor.

[0043] S3. Transfer the bone char precursor obtained in step S2 to an oven preheated to 275 °C and heat it for 3.5 h. Then increase the heating rate of the oven to 375 °C and heat it at 375 °C for 5 h, and dry it at 70 °C for 11 h to obtain pre-carbonized bone char.

[0044] S4. After grinding the pre-carbonized bone char obtained in step S3 for 30 min, transfer the pre-carbonized bone char to a crucible and place it in a tube furnace. Under an argon atmosphere with a gas flow rate of 0.4 L / min, heat it at a heating rate of 10 °C / min to 900 °C, and calcine it at 900 °C for 150 min. Cool it, grind it into components, wash it with hydrochloric acid and alcohol, and then dry it at 70 °C for 16 h to obtain sulfur-doped bone char, denoted as S / BBC900.

[0045] Example 3

[0046] This example provides a method for preparing sulfur-doped bone char, specifically as follows:

[0047] S1. Take animal bones with a phosphorus dry weight content of 20.09% and boil them in boiling water for 3 h. Let them air dry naturally, crush them, place them in a ball mill, and ball mill them for 240 min under the conditions of a ball-to-material ratio of 100:1 and a rotation speed of 800 r / min to obtain bovine bone powder with a particle size of 0.5 mm; mix 5 g of the obtained bone meal with 100 ml of ethanol, continuously stir it at a rotation speed of 800 r / min for 60 min, and then perform ultrasonic treatment for 30 min to obtain a bone meal slurry.

[0048] S2. Add 1.25 g of sodium polysulfide to the bone meal slurry obtained in step S1, and stir it at a constant temperature of 70 °C and 1000 r / min for 120 min to obtain a bone char precursor.

[0049] S3. Transfer the bone char precursor obtained in step S2 to an oven preheated to 250 °C and heat it for 4 h. Then increase the heating rate of the oven to 350 °C and heat it at 350 °C for 6 h, and dry it at 80 °C for 8 h to obtain pre-carbonized bone char.

[0050] S4. After grinding the pre-carbonized bone char obtained in step S3 for 40 min, transfer the pre-carbonized bone char to a crucible and place it in a tube furnace. Under a nitrogen atmosphere with a gas flow rate of 0.3 L / min, heat it at a heating rate of 15 °C / min to 950 °C, and calcine it at 950 °C for 120 min. Cool it, grind it into components, wash it with sulfuric acid and alcohol, and then dry it at 80 °C for 12 h to obtain sulfur-doped bone char, denoted as S / BBC950.

[0051] Example 4

[0052] A method for treating coking wastewater with peracetic acid in situ synthesized by activating animal bone char with sulfur, specifically as follows:

[0053] T1. Dissolve the S / BBC850 biochar prepared in Example 1 in dimethylformamide and ultrasonicate for 30 min. Vacuum filter the uniformly dispersed S / BBC850 biochar solution onto a polypropylene filter membrane. After alcohol washing, dry it at 80 °C for 12 h to obtain a sulfur-doped bone char filter membrane.

[0054] T2. Fix the sulfur-doped bone char filter membrane to the membrane module. Use coking wastewater containing tetraacetylethylenediamine and sodium percarbonate as the feed liquid. The concentration of tetraacetylethylenediamine in the feed liquid is 5 mM, and the concentration of sodium percarbonate is 5 mM. Use a circulation pump to perform a cyclic catalytic degradation reaction from top to bottom with a hydraulic driving force of 0.05 bar. Take the filtrate after the filter membrane at regular intervals for COD concentration testing, and the data is as shown in the appendix Figure 1 shown.

[0055] Use the same method to treat coking wastewater with S / BBC900 and S / BBC950, and perform COD concentration testing on the treated filtrate. The data is as shown in the appendix Figure 1 shown.

[0056] Example 5

[0057] This example provides a method for treating coking wastewater with peracetic acid in situ synthesized by activating sulfur-doped bone char of the present invention, specifically as follows:

[0058] T1. Dissolve the S / BBC850 biochar prepared in Example 1 in N,N-dimethylacetamide and ultrasonicate for 45 min. Vacuum filter the uniformly dispersed S / BBC850 biochar solution onto a polypropylene filter membrane. After alcohol washing, dry it at 70 °C for 16 h to obtain a sulfur-doped bone char filter membrane.

[0059] T2. Fix the sulfur-doped bone char filter membrane to the membrane module. Use coking wastewater containing tetraacetylethylenediamine and sodium percarbonate as the feed liquid. The concentration of tetraacetylethylenediamine in the feed liquid is 7.5 mM, and the concentration of sodium percarbonate is 7.5 mM. Use a circulation pump to perform a cyclic catalytic degradation reaction from top to bottom with a hydraulic driving force of 0.1 bar. Take the filtrate after the filter membrane at regular intervals for COD concentration testing, and the data is as shown in the appendix Figure 1 shown.

[0060] Use the same method to treat coking wastewater with S / BBC900 and S / BBC950, and perform COD concentration testing on the treated filtrate. The data is as shown in the appendix Figure 1 shown.

[0061] Example 6

[0062] This example provides a method for treating coking wastewater by in-situ synthesis of peracetic acid activated by sulfur-doped bone char of the present invention, specifically as follows:

[0063] T1. Dissolve the S / BBC850 biochar prepared in Example 1 in glycerol and ultrasonicate for 60 min. Vacuum filter the uniformly dispersed S / BBC850 biochar solution onto a polypropylene filter membrane. After alcohol washing, dry it at 60 °C for 20 h to obtain a sulfur-doped bone char filter membrane.

[0064] T2. Fix the sulfur-doped bone char filter membrane to the membrane module. Use the coking wastewater containing tetraacetylethylenediamine and sodium percarbonate as the feed liquid. The concentration of tetraacetylethylenediamine in the feed liquid is 10 mM, and the concentration of sodium percarbonate is 10 mM. Use a circulation pump with a hydraulic driving force of 0.1 bar to carry out a cyclic catalytic degradation reaction from top to bottom. Take the filtrate after the filter membrane at regular intervals for COD concentration testing, and the data is as shown in the appendix Figure 1 shown.

[0065] Use the same method to treat coking wastewater with S / BBC900 and S / BBC950, and conduct COD concentration testing on the treated filtrate. The data is as shown in the appendix Figure 1 shown.

[0066] It can be seen from Figure 1 that S / BBC900 has a better effect of activating peracetic acid to degrade COD in the biochemical effluent of coking wastewater than S / BBC950 and S / BBC850, and increasing the concentration of oxygen-based surfactants and peroxides is beneficial to the degradation of pollutants in coking wastewater.

[0067] The present invention uses sulfur-doped bone char to activate peracetic acid to treat coking wastewater. Compared with existing carbon materials, the sulfur-modified animal bone char material has a wide source, does not contain metal components, and has no secondary pollution problem. In addition, the sulfur-modified animal bone char combined with the membrane can activate in-situ generated peracetic acid, avoiding the safety problem of directly adding peracetic acid and the problem of effluent acidification, and is also beneficial to the recycling of sulfur-modified animal bone char.

Claims

1. A preparation method of a sulfur-doped bone char catalyst, characterized in that, The sulfur-doped bone char is bone char doped with sulfur elements; the preparation process includes the following steps: 1) Prepare bone powder slurry: Subject animal bones to high-temperature treatment, crush and grind them to obtain bone powder; mix the bone powder with a solvent, stir and ultrasonicate to obtain bone powder slurry; 2) Prepare bone char precursor powder: Add a sulfur-containing substance to the bone powder slurry obtained in step 1), stir at a constant temperature to obtain a bone char precursor; 3) Pre-carbonize the bone: Carry out a high-temperature pre-reaction on the bone char precursor obtained in step 2), wash with alcohol, and dry to obtain pre-carbonized bone char; 4) Prepare sulfur-doped bone char: Grind the pre-carbonized bone char obtained in step 3), calcine it under an inert atmosphere, grind it, wash it with acid, wash it with alcohol, and dry it to obtain sulfur-doped bone char.

2. The preparation method of a sulfur-doped bone char catalyst according to claim 1, characterized in that, In step 1), the phosphorus dry weight content in the animal bones is 17% - 21%.

3. The preparation method of a sulfur-doped bone char catalyst according to claim 1, characterized in that, In step 1), the high-temperature treatment is boiling in water for 1 - 3 h; the grinding is ball milling, and the ball milling conditions are: the ball milling speed is 600 - 800 r / min, the ball milling time is 120 - 240 min, and the ball-to-material ratio is 50 - 100:1; the particle size of the bone powder is 0.5 - 2.5 mm; The stirring is carried out at a speed of 600 - 800 r / min; the stirring time is 60 - 90 min; the ultrasonic time is 20 - 30 min.

4. The preparation method of a sulfur-doped bone char catalyst according to claim 1, characterized in that, In step 1), the bone powder is 3 - 5 g, and the solvent is deionized water or ethanol, with a dosage of 50 - 100 ml; in step 2), the sulfur-containing substance is sulfur powder, sodium polysulfide or sulfuric acid, the addition amount of sulfur powder or sodium polysulfide is 0.45 - 1.25 g, the mass concentration of sulfuric acid is 10% - 15%, and the addition amount is 15 - 20 ml.

5. The preparation method of a sulfur-doped bone char catalyst according to claim 1, characterized in that, In step 3), the high-temperature pre-reaction is heating in a high-temperature oven, and the heating conditions are: first heat at a temperature of 250 - 300 °C for 3 - 4 h, and then heat at a temperature of 350 - 400 °C for 4 - 6 h; the drying temperature is 60 - 80 °C, and the drying time is 10 - 12 h.

6. The preparation method of a sulfur-doped bone char catalyst according to claim 1, characterized in that, The calcination under an inert atmosphere in step 4) is calcination in a tubular furnace under an inert gas atmosphere. The inert gas is nitrogen, argon or helium, the gas flow rate is 0.3 - 0.5 L / min, the calcination temperature is 850 - 950 °C, the heating rate is 5 - 15 °C / min, and the calcination time is 2 - 3 h; the grinding time is 20 - 40 min; the acid used for acid washing is glacial acetic acid, hydrochloric acid or sulfuric acid; the drying temperature is 60 - 80 °C, and the drying time is 12 - 20 h.

7. The preparation method of a sulfur-doped bone char catalyst according to claim 1, characterized in that, In step 2), the conditions for constant-temperature stirring are: temperature 60 - 70 °C, stirring speed 1000 - 1200 r / min, and stirring time 120 - 180 min.

8. A method for treating coking wastewater by using a sulfur-doped bone char catalyst prepared by the preparation method according to any one of claims 1 to 7, characterized in that, Use sulfur-doped bone char to activate peracetic acid to treat the biochemical effluent of coking wastewater. The treatment method of the coking wastewater includes the following steps: 1) Prepare a sulfur-doped bone char filter membrane: Dissolve sulfur-doped bone char in an organic solvent, ultrasonically disperse it, vacuum filter the obtained sulfur-doped bone char dispersion onto a filter membrane, wash it with alcohol, and dry it to obtain a sulfur-doped bone char filter membrane; 2) Degradation reaction of coking wastewater: Fix the sulfur-modified bovine bone carbon filter membrane onto the membrane module, and use the coking wastewater added with oxygen-based surfactant and peroxide as the feed liquid to carry out a cyclic catalytic degradation reaction.

9. A method for treating coking wastewater according to claim 8, characterized in that, The organic solvent described in step 1) is one of dimethylformamide, N,N-dimethylacetamide, and glycerol; In the feed liquid described in step 2), the oxygen-based surfactant is tetraacetylethylenediamine with a concentration of 5 - 10 mM; the peroxide is sodium percarbonate with a concentration of 5 - 10 mM.

10. A method for treating coking wastewater according to claim 8, characterized in that, The feed liquid described in step 2) enters the reaction vessel in a top-down manner, and a water circulation is driven by a circulation pump in the reactor. The reaction time is 3 h - 6 h, and the output pressure of the circulation pump is 0.05 - 0.1 bar.

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