A heterogeneous catalytic material, its preparation method and application

Abstract

The invention discloses a heterogeneous catalytic material and a preparation method thereof, wherein the preparation method comprises the following steps: (1) Fenton sludge is subjected to pickling treatment to obtain a Fenton sludge pickling suspension, and then a magnesium salt solution and a manganese salt solution are added to obtain a mixed solution; (2) a chelating flocculant and a pH adjusting agent are added to the mixed solution obtained in step (1), and the reaction is followed by aging to obtain an aging liquid, the aging liquid is solid-liquid separated, and the obtained filter residue is washed and dried to obtain a catalytic material precursor; (3) the catalytic material precursor obtained in step (2) is mixed with asphalt, ball-milled and then roasted, cooled and then washed, and dried to obtain the heterogeneous catalytic material. The preparation method is simple, low in cost, and the catalytic performance of the obtained heterogeneous catalytic material is good, which greatly improves the resource utilization rate of Fenton sludge and solves the problems of complex process and high cost for preparing iron-based catalysts from Fenton sludge in the prior art.

Description

Technical Field

[0001] The present invention belongs to the technical field of solid waste treatment, and in particular relates to a heterogeneous catalytic material and a preparation method and application thereof. Background Art

[0002] During the recycling of retired batteries, battery wastewater containing a large amount of organic phosphorus will be generated. Due to the presence of organic phosphorus, the treatment of wastewater becomes more difficult and the treatment cost increases. Therefore, an economical and feasible method is needed to treat battery wastewater containing organic phosphorus. The Fenton method is an efficient wastewater treatment technology. Due to its strong oxidizing property, short reaction time and high degradation efficiency, it is often used in the deep treatment of wastewater. However, in the actual application of the Fenton method, due to its narrow pH application range and H 2 O 2 The low utilization rate, large amount of sludge produced in the reaction process, and the Fenton sludge rich in iron and some difficult-to-degrade organic matter produced are hazardous solid waste and cannot be properly disposed of, which to a certain extent limits its large-scale application.

[0003] At present, the main methods for disposing Fenton sludge are incineration, landfill and solidification treatment. These treatment methods have great limitations. On the one hand, Fenton sludge contains rich iron elements and has a high recycling value; on the other hand, Fenton sludge is a hazardous solid waste. During the incineration, landfill and solidification treatment process, it will produce waste gas, waste residue and waste liquid, which is easy to cause secondary pollution and pose a great potential danger to the environment. Therefore, seeking an economical and efficient Fenton sludge resource treatment method has become a research focus in this field. Summary of the invention

[0004] The present invention aims to solve at least one of the technical problems existing in the prior art. To this end, the present invention proposes a heterogeneous catalytic material and a preparation method and application thereof, wherein the heterogeneous catalytic material is prepared based on Fenton sludge, and the preparation method makes full use of the catalytic coupling mechanism between the Fe element and other active metal elements in the Fenton sludge to prepare the heterogeneous catalytic material, the preparation method is simple, the cost is low, and the catalytic performance of the prepared heterogeneous catalytic material is good, which greatly improves the resource utilization rate of Fenton sludge and solves the problems of complex process and high cost of preparing iron-based catalysts from Fenton sludge in the prior art.

[0005] The above technical objectives of the present invention are achieved through the following technical solutions:

[0006] A method for preparing a heterogeneous catalytic material comprises the following steps:

[0007] (1) performing an acid wash treatment on the Fenton sludge to obtain a Fenton sludge acid wash suspension, and then adding a magnesium salt solution and a manganese salt solution to obtain a mixed solution;

[0008] (2) adding a chelating flocculant and a pH regulator to the mixed solution obtained in step (1), aging the mixed solution after the reaction to obtain an aged solution, separating the aged solution into a solid-liquid mixture, washing the obtained filter residue and drying the residue to obtain a catalytic material precursor;

[0009] (3) The catalytic material precursor prepared in step (2) is mixed with asphalt, ball-milled and then calcined, cooled and then washed, and dried to obtain the heterogeneous catalytic material.

[0010] Preferably, in step (1), the Fenton sludge is dried, crushed and sieved before being subjected to the acid washing treatment.

[0011] Preferably, in step (1), the pickling treatment refers to mixing the Fenton sludge with acid solution and then placing it in a constant temperature water bath under stirring.

[0012] Preferably, in step (1), the concentration of the acid solution is 1%-5%, and the Fenton sludge and the acid solution are mixed in a volume ratio of 1:(5-15).

[0013] Further preferably, in step (1), the concentration of the acid solution is 2%-3%, and the Fenton sludge and the acid solution are mixed in a volume ratio of 1:(9-10).

[0014] Preferably, in step (1), the temperature of the constant temperature water bath is 50-80° C., and the stirring time in the constant temperature water bath is 0.5-2 h.

[0015] Further preferably, in step (1), the temperature of the constant temperature water bath is 60-70° C., and the stirring time in the constant temperature water bath is 1-1.5 h.

[0016] Preferably, the acid solution is at least one of sulfuric acid and hydrochloric acid.

[0017] Preferably, in step (1), the molar ratio of manganese ions, iron ions and magnesium ions in the mixed solution is 1:(0.8-3):(0.8-1.2).

[0018] Further preferably, in step (1), the molar ratio of manganese ions, iron ions and magnesium ions in the mixed solution is 1:(1-2):1.

[0019] Preferably, in step (2), the chelating flocculant is at least one of dithiocarboxylated hydroxymethyl polyacrylamide, dithiocarboxylated sulfomethyl polyacrylamide and dithiocarboxylated aminomethyl polyacrylamide.

[0020] Further preferably, in step (2), the chelating flocculant is dithiocarboxylated amine methyl polyacrylamide.

[0021] Preferably, in step (2), the pH regulator is aqueous ammonia with a mass fraction of 5%-10%.

[0022] Further preferably, in step (2), the pH adjuster is aqueous ammonia with a mass fraction of 5%-7%.

[0023] Preferably, in step (2), the reaction temperature is 50-70°C.

[0024] Further preferably, in step (2), the reaction temperature is 55-65°C.

[0025] Preferably, in step (2), the chelating flocculant and the pH adjusting agent are added dropwise. When the pH of the mixed solution is stabilized between 9.8 and 10.5, the mixture is stirred for reaction for 2 to 4 hours and then allowed to stand for 10 to 15 hours to obtain the aged solution.

[0026] Further preferably, in step (2), the chelating flocculant and the pH adjusting agent are added dropwise, and when the pH of the mixed solution is stabilized between 9.8-10, the mixture is stirred for reaction for 3 hours, and then allowed to stand for 12 hours to obtain the aged solution.

[0027] Preferably, in step (2), the filter residue washing refers to washing the filter residue with water until the pH of the waste water after washing is neutral and then drying it.

[0028] Preferably, in step (3), the amount of asphalt added is 10%-30%.

[0029] Further preferably, in step (3), the amount of asphalt added is 10%-20%. A uniform layer of carbonaceous material is coated on the surface of the formed monomer structure by ball milling and mixing, and then a part of the asphalt coated on the surface is decomposed by pyrolysis reaction to form a stable porous carbonaceous structure on the surface of the catalytic material, which can enhance the stability of the spatial structure of the catalytic material and the cycle life.

[0030] Preferably, in step (3), the ball milling time is 0.5-1 h, and the ball milling speed is 300-400 rpm.

[0031] Preferably, in step (3), the calcination conditions are: under an inert atmosphere, heating to 300-400°C at a heating rate of 3-10°C / min, maintaining the temperature for 2-3h, then heating to 500-550°C at a heating rate of 3-10°C / min, maintaining the temperature for 1-2h.

[0032] Further preferably, in step (3), the calcination conditions are: under an inert atmosphere, heating to 300-350°C at a heating rate of 3-5°C / min, maintaining the temperature for 2-3h, then heating to 500-550°C at a heating rate of 3-5°C / min, maintaining the temperature for 1-2h.

[0033] Preferably, in step (3), the cleaning is first performed with a dilute acid solution having a concentration of 0.5%-1%, then with water, and then dried after the pH of the waste water after cleaning is neutral.

[0034] A heterogeneous catalytic material is prepared by the preparation method as described above.

[0035] The heterogeneous catalytic materials described above are used to treat wastewater containing organic phosphorus.

[0036] The Fe in Fenton sludge is mainly in the form of ferric oxyhydroxide (FeOOH) and ferric hydroxide (Fe(OH) 3 ) exists in the form of, after being calcined at a certain temperature, dehydrogenation reaction occurs to form Fe 3 O 4 It has magnetic separation properties. In this process, by doping with other elements and controlling the reaction conditions, different structures can be formed, such as:

[0037] Mn(OH) 2 +Fe(OH) 3 →MnFe 2 O 4 +H 2 O

[0038] After calcination, a Mn(II) / Fe(III) heterogeneous structure system is formed, and electron transfer occurs between the two to catalyze H 2 O 2 Produces a large amount of ·OH and ·O 2 -Free radicals can degrade organic phosphorus in wastewater into free inorganic phosphorus; the MgO nanostructure formed on the surface of the catalytic material can then be used to achieve super-enrichment adsorption of inorganic phosphorus, thereby achieving the removal of phosphorus from wastewater.

[0039] The beneficial effects of the present invention are:

[0040] (1) The present invention firstly dissolves the metal elements in the Fenton sludge by acid washing, adds a certain amount of Mn and Mg solution, and then adds a chelating flocculant and a pH regulator. On the one hand, the chelating flocculant can be used to form a stable chelate with the metal ions, which has the ability to chelate and remove heavy metals and has a flocculation and sedimentation effect; on the other hand, the chelating flocculant can be introduced as a carbon source, and in the subsequent high-temperature pyrolysis reaction process, the high-valent metal ions (Fe 3+ , Mn4+ Reduction to Fe 2+ , Mn 2 + ), enhancing the catalytic performance of the catalytic material; furthermore, by adjusting the mixed solution to a specific pH through a pH regulator, the stability of the chelate formed by the chelating flocculant and the metal ion is enhanced.

[0041] (2) The present invention adopts pyrolysis technology to prepare magnetic MnFe 2 O 4 Crystal structure catalytic materials can increase the specific surface area of ​​catalytic materials, increase the surface area of ​​pollutants and MnFe inside the coating layer 2 O 4 The contact area of ​​the structural monomers is used to generate mobile e-catalytic H between Fe(III) / Mn(II) 2 O 2 A large amount of ·OH is generated to degrade organic matter in wastewater and improve the catalytic performance of the material. On the other hand, the surface carbon coating technology is used to coat a uniform layer of carbonaceous material on the surface of the formed monomer structure by ball milling and mixing. Through the pyrolysis reaction, part of the organic matter in the surface-coated asphalt is decomposed to form a porous structure, and the chelating flocculant (dithiocarboxylated aminomethyl polyacrylamide) in the internally coated catalytic material undergoes a decomposition reaction under high temperature conditions, reducing part of the high-valent metal ions in the catalytic material and generating a large amount of gas, further increasing the specific surface area of ​​the catalytic material. In addition, a layer of stable carbonaceous structure is formed on the surface of the catalytic material after pyrolysis, which can enhance the stability of the spatial structure of the catalytic material and the cycle life.

[0042] (3) The heterogeneous catalytic material prepared by Fenton sludge in the present invention has good magnetic properties. Magnetic separation technology can be used in the secondary recovery process to improve separation efficiency and recovery efficiency. The catalytic material can be used as a phosphorus removal adsorption material in the treatment process of wastewater containing organic phosphorus, which is conducive to achieving the goal of "treating waste with waste" and meets the development requirements of the circular economy. BRIEF DESCRIPTION OF THE DRAWINGS

[0043] Figure 1 This is a schematic diagram of the process for preparing a heterogeneous catalytic material according to Example 1 of the present invention;

[0044] Figure 2 This is a flow chart of the overall synthesis of heterogeneous catalytic materials according to Example 1 of the present invention;

[0045] Figure 3 This is a monomer composite structure diagram of the heterogeneous catalytic material of Example 1 of the present invention. DETAILED DESCRIPTION

[0046] The present invention will be further described below in conjunction with specific embodiments.

[0047] Embodiment 1:

[0048] A method for preparing a heterogeneous catalytic material, such as Figure 1 and Figure 2 As shown, the following steps are included:

[0049] (1) drying, crushing and sieving the Fenton sludge to obtain Fenton sludge powder;

[0050] (2) Fenton sludge powder was mixed with 2% hydrochloric acid solution in a volume ratio of 1:10, and pickled in a constant temperature water bath at 60°C. After stirring for 1.5 hours, a Fenton sludge pickled suspension was obtained;

[0051] (3) adding a magnesium chloride solution and a manganese chloride solution dropwise to the obtained suspension at a molar ratio of manganese ion: iron ion: magnesium ion of 1:2:1, and stirring the mixture for 1 hour to obtain a mixed solution;

[0052] (4) slowly adding 2% by mass of DTAPAM (dithiocarboxylated aminomethyl polyacrylamide) solution and 5% ammonia water to the mixed solution obtained in step (3), maintaining the reaction temperature at 55° C. until the pH value of the mixed solution stabilizes at 9.8, continuing to slowly stir the reaction for 3 hours, and then standing for 12 hours to obtain an aged solution;

[0053] (5) After the aged liquid is subjected to a solid-liquid separation operation, the obtained filter residue is washed with water until the pH value is neutral, and then dried to obtain a catalytic material precursor;

[0054] (6) The catalyst material precursor and asphalt are mixed at a mass ratio of 1:9, and the asphalt is evenly coated on the surface of the catalyst material precursor by ball milling (ball milling time is 1 h, and the number of revolutions is 300 rpm);

[0055] (7) The sample material was placed in an atmosphere furnace for pyrolysis. The calcination conditions were: heating rate 5 °C / min, constant temperature 350 °C, constant temperature 2 h, N 2 atmosphere; then raise the temperature to 500°C, the heating rate is 5°C / min, keep the temperature constant for 1h, N 2 Atmosphere, after the pyrolysis reaction is completed, wait for it to cool to room temperature and take out the sample;

[0056] (8) The sample is first washed with a 0.5% dilute hydrochloric acid solution, then washed with water until the pH is neutral, and then dried and ground to obtain a magnetic porous heterogeneous catalytic material.

[0057] A heterogeneous catalytic material is prepared by the above preparation method. The monomer composite structure of the prepared heterogeneous catalytic material is shown in FIG. Figure 3 shown.

[0058] Embodiment 2:

[0059] A method for preparing a heterogeneous catalytic material comprises the following steps:

[0060] (1) drying, crushing and sieving the Fenton sludge to obtain Fenton sludge powder;

[0061] (2) Fenton sludge powder was mixed with 2% hydrochloric acid solution in a volume ratio of 1:10, and pickled in a constant temperature water bath at 60°C. After stirring for 1.5 hours, a Fenton sludge pickled suspension was obtained;

[0062] (3) adding a magnesium chloride solution and a manganese chloride solution dropwise to the obtained suspension at a molar ratio of manganese ion: iron ion: magnesium ion of 1:2:1, and stirring the mixture for 1 hour to obtain a mixed solution;

[0063] (4) slowly adding 2% by mass of DTAPAM (dithiocarboxylated aminomethyl polyacrylamide) solution and 5% ammonia water to the mixed solution obtained in step (3), maintaining the reaction temperature at 60° C. until the pH value of the mixed solution stabilizes at 9.8, continuing to slowly stir the reaction for 3 hours, and then standing for 12 hours to obtain an aged solution;

[0064] (5) After the aged liquid is subjected to a solid-liquid separation operation, the obtained filter residue is washed with water until the pH value is neutral, and then dried to obtain a catalytic material precursor;

[0065] (6) The catalyst material precursor and asphalt are mixed at a mass ratio of 1:9, and the asphalt is evenly coated on the surface of the catalyst material precursor by ball milling (ball milling time is 1 h, and the number of revolutions is 300 revolutions / min);

[0066] (7) The sample material was placed in an atmosphere furnace for pyrolysis. The calcination conditions were: heating rate 5 °C / min, constant temperature 300 °C, constant temperature 2 h, N 2 atmosphere; then raise the temperature to 550°C, the heating rate is 5°C / min, keep the temperature constant for 1h, N 2 Atmosphere, after the pyrolysis reaction is completed, wait for it to cool to room temperature and take out the sample;

[0067] (8) The sample is first washed with a 0.5% dilute hydrochloric acid solution, then washed with water until the pH is neutral, and then dried and ground to obtain a magnetic porous heterogeneous catalytic material.

[0068] A heterogeneous catalytic material is prepared by the above preparation method.

[0069] Embodiment 3:

[0070] A method for preparing a heterogeneous catalytic material comprises the following steps:

[0071] (1) drying, crushing and sieving the Fenton sludge to obtain Fenton sludge powder;

[0072] (2) Fenton sludge powder was mixed with 2% hydrochloric acid solution in a volume ratio of 1:10, and pickled in a constant temperature water bath at 60°C. After stirring for 1.5 hours, a Fenton sludge pickled suspension was obtained;

[0073] (3) adding a magnesium chloride solution and a manganese chloride solution dropwise to the obtained suspension at a molar ratio of manganese ion: iron ion: magnesium ion of 1:1:1, and stirring the mixture for 1 hour to obtain a mixed solution;

[0074] (4) slowly adding 2% by mass of DTMPAM (dithiocarboxylated hydroxymethyl polyacrylamide) solution and 7% ammonia water to the mixed solution obtained in step (3), maintaining the reaction temperature at 60° C. until the pH value of the mixed solution stabilizes at 10, continuing to slowly stir the reaction for 3 hours, and then standing for 12 hours to obtain an aged solution;

[0075] (5) After the aged liquid is subjected to a solid-liquid separation operation, the obtained filter residue is washed with water until the pH value is neutral, and then dried to obtain a catalytic material precursor;

[0076] (6) The catalyst material precursor and asphalt are mixed in a mass ratio of 1.5:8.5, and the asphalt is evenly coated on the surface of the catalyst material precursor by ball milling (ball milling time is 1 h, and the number of revolutions is 300 rpm);

[0077] (7) The sample material was placed in an atmosphere furnace for pyrolysis. The calcination conditions were: heating rate 5 °C / min, constant temperature 350 °C, constant temperature 2 h, N 2 atmosphere; then raise the temperature to 550°C, the heating rate is 5°C / min, keep the temperature constant for 1h, N 2 Atmosphere, after the pyrolysis reaction is completed, wait for it to cool to room temperature and take out the sample;

[0078] (8) The sample is first washed with a 0.5% dilute hydrochloric acid solution, then washed with water until the pH is neutral, and then dried and ground to obtain a magnetic porous heterogeneous catalytic material.

[0079] A heterogeneous catalytic material is prepared by the above preparation method.

[0080] Embodiment 4:

[0081] A method for preparing a heterogeneous catalytic material comprises the following steps:

[0082] (1) drying, crushing and sieving the Fenton sludge to obtain Fenton sludge powder;

[0083] (2) Fenton sludge powder was mixed with 3% sulfuric acid solution in a volume ratio of 1:9, and pickled in a constant temperature water bath at 70°C. After stirring for 1 hour, a Fenton sludge pickled suspension was obtained;

[0084] (3) adding a magnesium chloride solution and a manganese chloride solution dropwise to the obtained suspension at a molar ratio of manganese ion: iron ion: magnesium ion of 1:1:1, and stirring the mixture for 1 hour to obtain a mixed solution;

[0085] (4) slowly adding 2% by mass of DTSPAM (dithiocarboxylated sulfomethyl polyacrylamide) solution and 10% ammonia water to the mixed solution obtained in step (3), maintaining the reaction temperature at 65° C. until the pH value of the mixed solution stabilizes at 10, continuing to slowly stir the reaction for 3 hours, and then standing for 12 hours to obtain an aged solution;

[0086] (5) After the aged liquid is subjected to a solid-liquid separation operation, the obtained filter residue is washed with water until the pH value is neutral, and then dried to obtain a catalytic material precursor;

[0087] (6) The catalyst material precursor and asphalt are mixed in a mass ratio of 2:8, and the asphalt is evenly coated on the surface of the catalyst material precursor by ball milling (ball milling time is 0.5 h, and the number of revolutions is 400 rpm);

[0088] (7) The sample material was placed in an atmosphere furnace for pyrolysis. The calcination conditions were: heating rate 5 °C / min, constant temperature 400 °C, constant temperature 2 h, N 2 atmosphere; then raise the temperature to 550°C, the heating rate is 5°C / min, keep the temperature constant for 1h, N 2 Atmosphere, after the pyrolysis reaction is completed, wait for it to cool to room temperature and take out the sample;

[0089] (8) The sample is first washed with a 0.5% dilute hydrochloric acid solution, then washed with water until the pH is neutral, and then dried and ground to obtain a magnetic porous heterogeneous catalytic material.

[0090] A heterogeneous catalytic material is prepared by the above preparation method.

[0091] Comparative Example 1: (Compared with Example 1, the difference is that after pretreatment, only magnesium loading and pyrolysis reactions are performed)

[0092] A method for preparing a catalytic material comprises the following steps:

[0093] (1) drying, crushing and sieving the Fenton sludge to obtain Fenton sludge powder;

[0094] (2) Uniformly disperse the Fenton sludge powder in the magnesium chloride solution (with a molar ratio of iron ions to magnesium ions of 2:1), slowly add 5% ammonia water dropwise, and continuously stir the reaction slowly. Control the pH of the reaction system to be 9.8, the reaction temperature to be 55 °C, and the reaction time to be 3 h. After the reaction is completed, perform solid-liquid separation and dry the filter residue to obtain the sample material;

[0095] (3) Place the sample material in an atmosphere furnace for pyrolysis. The roasting conditions are: heating rate of 5 °C / min, constant temperature of 350 °C, constant temperature for 2 h, N 2 atmosphere; then raise the temperature to 500 °C, heating rate of 5 °C / min, constant temperature for 1 h, N 2 atmosphere. After the pyrolysis reaction is completed, wait until it cools to room temperature and take out the sample;

[0096] (4) First wash the sample with a 0.5% dilute acid solution, then wash it with water until the pH is neutral, and then dry and grind it to obtain the catalytic material.

[0097] Comparative Example 2: (Compared with Example 1, the difference is that after pretreatment, only manganese loading and surface coating are carried out)

[0098] A preparation method of a catalytic material, comprising the following steps:

[0099] (1) After drying, crushing, and sieving the Fenton sludge, obtain the Fenton sludge powder;

[0100] (2) Mix the Fenton sludge powder with a 2% hydrochloric acid solution at a volume ratio of 1:10, and carry out pickling treatment in a constant temperature water bath at 60 °C. After stirring and reacting for 1.5 h, obtain the Fenton sludge pickling suspension;

[0101] (3) Slowly and synchronously add the manganese chloride solution to the suspension according to the molar ratio of manganese ions to iron ions of 1:2, and continuously stir and react for 1.5 h to obtain the mixed solution;

[0102] (4) Slowly add 5% ammonia water by mass fraction to the mixed solution, keep the reaction temperature at 55 °C until the pH of the mixed solution stabilizes at 9.8, continue to stir and react slowly for 3 h, and then let it stand for aging for 12 h to obtain the aging solution;

[0103] (5) After performing solid-liquid separation on the aging solution, wash the obtained filter residue with water until the pH is neutral, and then dry it to obtain the catalytic material precursor;

[0104] (6) Mix the catalytic material precursor with asphalt at a mass ratio of 1:9, and use ball milling (ball milling time is 1 h, rotation speed is 300 r / min) to uniformly coat the asphalt on the surface of the catalytic material precursor to obtain the catalytic material.

[0105] Comparative Example 3: (Compared with Example 1, the difference is that after pretreatment, only manganese loading, surface coating and pyrolysis reaction are performed)

[0106] A method for preparing a catalytic material comprises the following steps:

[0107] (1) drying, crushing and sieving the Fenton sludge to obtain Fenton sludge powder;

[0108] (2) Fenton sludge powder was mixed with 2% hydrochloric acid solution in a volume ratio of 1:10, and pickled in a constant temperature water bath at 60°C. After stirring for 1.5 hours, a Fenton sludge pickled suspension was obtained;

[0109] (3) slowly and synchronously adding a manganese chloride solution to the suspension at a molar ratio of manganese ions to iron ions of 1:2, and continuously stirring the mixture for 1 hour to obtain a mixed solution;

[0110] (4) slowly adding 5% ammonia water to the mixed solution, maintaining the reaction temperature at 55° C. until the pH value of the mixed solution stabilizes at 9.8, continuing to slowly stir the reaction for 3 h, and then allowing to stand for 12 h to obtain an aged solution;

[0111] (5) After the aged liquid is subjected to a solid-liquid separation operation, the obtained filter residue is washed with water until the pH value is neutral, and then dried to obtain a catalytic material precursor;

[0112] (6) The catalyst material precursor and asphalt are mixed at a mass ratio of 1:9, and the asphalt is evenly coated on the surface of the catalyst material precursor by ball milling (ball milling time is 1 h, and the number of revolutions is 300 rpm);

[0113] (7) The sample material was placed in an atmosphere furnace for pyrolysis. The calcination conditions were: heating rate 5 °C / min, constant temperature 350 °C, constant temperature 2 h, N 2 atmosphere; then raise the temperature to 500°C, the heating rate is 5°C / min, keep the temperature constant for 1h, N 2 Atmosphere, after the pyrolysis reaction is completed, wait for it to cool to room temperature and take out the sample;

[0114] (8) The sample is first washed with a 0.5% dilute hydrochloric acid solution, then washed with water until the pH is neutral, and then dried and ground to obtain a catalytic material.

[0115] Test example:

[0116] 1. The specific surface areas of the heterogeneous catalytic materials of Examples 1-4 and the catalytic materials of Comparative Examples 1-3 were measured respectively. The measurement results are shown in Table 1.

[0117] 2. Phosphorus removal test: Take 0.03 g of the heterogeneous catalytic material of Examples 1-4 and the catalytic material of Comparative Examples 1-3, respectively, and add them into 100 mL of simulated organic phosphorus wastewater with a concentration of 100 mg / L and pH = 3.5, then add 1 mL of 30% hydrogen peroxide, stir and react for 3 hours. After the reaction is completed, filter out the catalytic material, measure the residual phosphorus content in the water, and calculate the phosphorus removal rate. The test results are shown in Table 1.

[0118] 3. Repeat the phosphorus removal test 5 times. After each test, the heterogeneous catalytic materials of Examples 1-4 and the catalytic materials of Comparative Examples 1-3 were cleaned with a 1:1 mixture of 0.5 mol / L HCl solution and 0.5 mol / L NaCl solution. The cleaned catalytic materials were filtered and washed, vacuum dried, and recycled. The reuse effect of the catalytic materials was detected each time, and the phosphorus removal rate of the fifth time was recorded. The test results are shown in Table 1.

[0119] Table 1: Experimental results

[0120]

[0121] As shown in Table 1, the specific surface area of ​​the heterogeneous catalytic material prepared by the preparation method of the present invention reaches 308.79 m 2 / g, the first maximum equilibrium removal amount reached more than 268.27 mg / g, the first phosphorus removal rate reached more than 80.48%, and when recycled, the fifth phosphorus removal rate reached more than 63.47%.

[0122] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.

Claims

1. A preparation method of a heterogeneous catalytic material, characterized in that: it includes the following steps: (1) Pickle Fenton sludge to obtain a pickled suspension of Fenton sludge, and then add a magnesium salt solution and a manganese salt solution to obtain a mixed solution; (2) Add a chelating flocculant and a pH regulator to the mixed solution prepared in step (1), react and then age to obtain an aged solution. Separate the solid and liquid of the aged solution, wash the obtained filter residue and dry it to obtain a catalytic material precursor; (3) Mix the catalytic material precursor prepared in step (2) with asphalt, ball mill and then calcine, wash after cooling, and dry to obtain the heterogeneous catalytic material; In step (2), the chelating flocculant is at least one of carboxymethylated polyacrylamide dithiocarboxylate, sulfomethylated polyacrylamide dithiocarboxylate, and aminomethylated polyacrylamide dithiocarboxylate.

2. The preparation method of a heterogeneous catalytic material according to claim 1, characterized in that: In step (1), the molar ratio of manganese ions, iron ions and magnesium ions in the mixed solution is 1:(0.8 - 3):(0.8 - 1.2).

3. The preparation method of a heterogeneous catalytic material according to claim 1, characterized in that: In step (2), the pH regulator is ammonia water with a mass fraction of 5% - 10%.

4. The preparation method of a heterogeneous catalytic material according to claim 1, characterized in that: In step (2), the reaction temperature is 50 - 70 °C.

5. The preparation method of a heterogeneous catalytic material according to claim 1, characterized in that: In step (2), the chelating flocculant and the pH regulator are added dropwise. After the pH in the mixed solution is stabilized between 9.8 - 10.5, continue to stir and react for 2 - 4 h, and then stand and age for 10 - 15 h to obtain the aged solution.

6. The preparation method of a heterogeneous catalytic material according to claim 1, characterized in that: In step (3), the addition amount of asphalt is 10% - 30%.

7. The preparation method of a heterogeneous catalytic material according to claim 1, characterized in that: In step (3), the calcination conditions are: under an inert atmosphere, raise the temperature to 300 - 400 °C at a heating rate of 3 - 10 °C / min, keep the temperature constant for 2 - 3 h, and then raise the temperature to 500 - 550 °C at a heating rate of 3 - 10 °C / min, and keep the temperature constant for 1 - 2 h.

8. A heterogeneous catalytic material, characterized in that: the heterogeneous catalytic material is prepared by the preparation method described in any one of claims 1 - 7.

9. Application of the heterogeneous catalytic material according to claim 8 in treating organic phosphorus wastewater.

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