Preparation method and application of waste manganese slag carbon-based composite material for controlling and inhibiting antimony

Abstract

The application discloses a preparation method of a waste manganese slag carbon-based composite material for blocking and controlling antimony, and the method is as follows: waste electrolytic manganese slag is placed in a cracking furnace, and is fired at a high temperature of 550 DEG C for 2 hours; after cooling, the electrolytic manganese slag is ground to 100 meshes; corn straw powder is placed in the cracking furnace, and is cracked at a high temperature of 550 DEG C for 2 hours to obtain biochar, and then the biochar is ground to 100 meshes for use. Finally, the ground biochar and the electrolytic manganese slag are mixed according to a mass ratio of 1:1, and 6 times of the total mass of the biochar and the electrolytic manganese slag in deionized water is added for ball milling; the well-milled biochar and manganese slag mixture is naturally precipitated, the surface liquid is removed, and a moist solid precipitate is obtained; then the moist solid precipitate is placed in an oven and dried at 45 DEG C to obtain a manganese slag carbon-based composite material. The application not only strengthens the blocking and controlling ability of biochar to antimony pollution by using waste manganese slag, but also realizes resource utilization of the waste manganese slag, greatly reduces the production cost of the passivation material, and can realize the purpose of large-area use.

Description

Technical Field

[0001] This invention belongs to the field of environmental remediation technology, specifically relating to a method for preparing and applying a carbon-based composite material for controlling antimony in waste manganese slag. Background Technology

[0002] Currently, there are physical / chemical remediation technologies, biological remediation technologies, and agricultural ecological remediation technologies for the treatment of antimony pollution. However, due to factors such as economic value and practical application, solidification / stabilization technology has become the main method for antimony pollution treatment. The main approach is to use soil passivating agents to solidify antimony in the soil. Therefore, the development of low-cost passivating materials that can be used on a large scale has become a bottleneck problem in the current treatment of antimony pollution in soil. Summary of the Invention

[0003] The technical problem to be solved by the present invention is to provide a method for preparing and applying a carbon-based composite material of waste manganese slag that controls antimony, which addresses the shortcomings of the prior art. This method utilizes waste manganese slag to realize the resource utilization of manganese slag waste, significantly reduces the production cost of passivation materials, and enables large-scale application.

[0004] The technical solution of the present invention is: a method for preparing a carbon-based composite material of waste manganese slag with antimony-controlling properties, characterized in that: the method includes: mixing ground biochar and pyrolytic manganese slag at a mass ratio of 1:1, then placing them in a ball mill jar, adding deionized water at a mass ratio of not less than 6 times the total mass of biochar and electrolytic manganese slag, and ball milling with mixed stainless steel grinding balls of three different diameters of 15, 25 and 35 mm, allowing the ball-milled mixture to undergo natural sedimentation to remove the surface liquid and obtain a moist solid precipitate, which is then placed in an oven to dry, thereby obtaining the carbon-based composite material of waste manganese slag.

[0005] Preferably, the ball milling speed is 150 r / min and the time is 8 h.

[0006] Preferably, the drying time is 80°C.

[0007] Preferably, the mass ratio of stainless steel grinding balls with three different diameters of 15, 25, and 35 mm is 1:1:1; the mass ratio of the total mass of biochar and electrolytic manganese slag to the mass of the mixed stainless steel grinding balls is 1:20.

[0008] Preferably, the waste manganese slag is placed in a pyrolysis furnace and calcined at a high temperature of 550°C for 2 hours, and then cooled to obtain pyrolytic manganese slag; corn stalks are pulverized and placed in a pyrolysis furnace, and pyrolyzed at a high temperature of 550°C for 2 hours under nitrogen protection to obtain biochar.

[0009] Preferably, the biochar and pyrolytic manganese slag are ground to 100 mesh.

[0010] In addition, the present invention also discloses an application of the antimony-controlling waste manganese slag carbon-based composite material prepared according to the above method, characterized in that: the antimony-controlling waste manganese slag carbon-based composite material is used to control antimony pollution in soil.

[0011] Compared with the prior art, the present invention has the following advantages:

[0012] 1. This invention is based on the adsorption and complexation of antimony by iron-manganese materials in manganese slag, combined with the alkaline properties of biochar. This avoids the release of other heavy metals from the manganese slag and reduces the activity of antimony in the soil, ensuring the safety of the product. Furthermore, this invention utilizes waste manganese slag to achieve resource utilization of manganese slag, significantly reducing the production cost of passivation materials and enabling large-scale application.

[0013] 2. This invention significantly broadens the application scope of existing Sb-contaminated soil remediation materials: In the original simple biochar remediation of antimony-contaminated soil, the optimal environmental medium for biochar to exhibit a significant passivation effect on antimony is a pH value of around 2-3. When the environmental medium is under other acidic or alkaline conditions, the passivation effect of biochar on antimony is not very obvious. Clearly, compared to current Sb-contaminated soil passivation materials, the passivation material prepared in this invention significantly broadens the application scope of existing Sb pollution remediation materials.

[0014] 3. The waste manganese slag carbon-based composite material prepared in this invention significantly enhances the adsorption capacity of existing passivation materials for antimony: At the optimal dosage of 0.1g adsorbent, compared to biochar, the biochar-manganese slag composite material shows a significant improvement in both adsorption capacity per unit amount and removal efficiency for antimony. Biochar has an adsorption capacity of 511.83 mg / g and a removal efficiency of 17.76%, while the biochar-manganese slag composite material has an adsorption capacity of 2451.47 mg / g and a removal efficiency of 85.08%. Clearly, the biochar-manganese slag composite material exhibits excellent adsorption capacity and adsorption ability for antimony.

[0015] 4. Resource utilization of electrolytic manganese slag and agricultural waste straw has been achieved: Electrolytic manganese slag is the waste residue generated during a series of production processes in the preparation of metallic manganese products, including acid leaching, oxidation, ammonia neutralization, pressure filtration, electrolysis, passivation, cleaning, and drying of manganese ore. Statistics show that 8-9 tons of electrolytic manganese slag are emitted for every ton of electrolytic manganese produced. Most electrolytic manganese production enterprises in my country transport the waste slag to stockpiles and construct dams for wet storage. However, electrolytic manganese slag is classified as general industrial solid waste, and its stockpiling sites must meet the corresponding national standards for industrial solid waste treatment sites. Some electrolytic manganese production enterprises directly stockpile the generated waste slag in substandard and poorly constructed stockpiles. This is not only a huge waste of land resources, but also because electrolytic manganese slag contains a large number of pollutants, such as manganese ions and ammonia nitrogen, which can easily enter the soil, surface water, and groundwater through leachate. The long-term release of these pollutants could potentially cause safety hazards and serious environmental pollution. This invention uses electrolytic waste manganese slag as raw material. After pyrolysis, it is mixed with biochar and ball-milled to prepare a carbon-based manganese slag composite material, which can effectively realize the resource utilization of waste manganese slag and reduce its harm to soil and groundwater.

[0016] The technical solution of the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. Attached Figure Description

[0017] Figure 1 This is a bar chart showing the physicochemical properties of six materials prepared in Example 1 of this invention: biochar (BC), pyrolytic manganese slag (MZ), biochar-manganese slag composite material (BM), waste manganese slag carbon-based composite material (QBM), ball milled manganese slag prepared in Comparative Example 1 (QMZ), and ball milled manganese slag-ground biochar prepared in Comparative Example 2 (QBC). In the figure, a represents pH; b represents EC; c represents Size; d represents CEC; e represents Zeta; and f represents Inorganic.

[0018] Figure 2 This is a graph showing the heavy metal leaching data of six materials prepared in Example 1 of this invention: biochar (BC), pyrolytic manganese slag (MZ), biochar-manganese slag composite material (BM), waste manganese slag carbon-based composite material (QBM), ball milled manganese slag prepared in Comparative Example 1 (QMZ), and ball milled manganese slag-ground biochar prepared in Comparative Example 2 (QBC).

[0019] Figure 3 This is a bar chart showing the ammonia nitrogen leaching of six materials prepared in Example 1 of this invention: biochar (BC), pyrolytic manganese slag (MZ), biochar-manganese slag composite material (BM), waste manganese slag carbon-based composite material (QBM), ball milled manganese slag prepared in Comparative Example 1 (QMZ), and ball milled manganese slag-ground biochar prepared in Comparative Example 2 (QBC).

[0020] Figure 4The bar charts showing the adsorption of ammonia nitrogen by biochar (BC) prepared in Example 1 of this invention and ball-milled manganese slag biochar (QBC) prepared in Comparative Example 2.

[0021] Figure 5 This is a bar chart showing the Sb(V) removal rate and adsorption capacity of six materials prepared in Example 1 of this invention: biochar (BC), pyrolytic manganese slag (MZ), biochar-manganese slag composite material (BM), waste manganese slag carbon-based composite material (QBM), ball milled manganese slag prepared in Comparative Example 1 (QMZ), and ball milled manganese slag-bought biochar prepared in Comparative Example 2 (QBC). Detailed Implementation Example 1

[0022] This embodiment discloses a method for preparing a carbon-based composite material of waste manganese slag with controlled antimony emission. The method is as follows:

[0023] S1. Place the waste manganese slag in a pyrolysis furnace and calcine it at a high temperature of 550℃ for 2 hours. After cooling, obtain pyrolytic manganese slag (marked as MZ) and grind it to 100 mesh for later use.

[0024] S2. After pulverizing the corn stalks, place them in a pyrolysis furnace and pyrolyze them at 11 °C·min under nitrogen protection. -1 The temperature was increased to 550℃ and pyrolyzed for 2 hours. After cooling, biochar (labeled as BC) was obtained and then ground to 100 mesh for later use.

[0025] S3. Grind the biochar and pyrolytic manganese slag in a 1:1 mass ratio to prepare a biochar-manganese slag composite material (labeled BM). Then, place it in a ball mill jar and add 6 times the total mass of deionized water of the biochar and electrolytic manganese slag. Use three different diameter stainless steel grinding balls of 15, 25 and 35 mm in a mass ratio of 1:1:1 to ball mill the mixture. After natural sedimentation, remove the surface liquid to obtain a moist solid precipitate. Then, place it in an oven and dry it at 80°C to obtain a waste manganese slag carbon-based composite material (labeled QBM).

[0026] In this embodiment, 50g of biochar and 50g of deionized water are used in S3, and 600mL of deionized water is used. Approximately 2kg of stainless steel grinding balls are used. The grinding jar is a stainless steel grinding jar, and the grinding mill GQM-4-5 is manufactured by Changsha Tianchuang Powder Technology Co., Ltd.

[0027] Comparative Example 1

[0028] Take 100g of the pyrolytic manganese slag (MZ) prepared in S1 of Example 1, place it in a ball mill jar, add 600mL of deionized water, and ball mill it with a mixture of stainless steel grinding balls of three different diameters (15, 25, and 35mm) weighing approximately 2kg. After the mixture is ball-milled, it undergoes natural sedimentation to remove the surface liquid, resulting in a moist solid precipitate. Then, it is placed in an oven and dried at 80°C to obtain ball-milled manganese slag (labeled QMZ).

[0029] Comparative Example 2

[0030] Take 100g of the biochar (BC) residue prepared in S2 of Example 1, place it in a ball mill jar, add 600mL of deionized water, and ball mill it with a mixture of stainless steel grinding balls of three different diameters (15, 25, and 35mm) weighing approximately 2kg. After the mixture is ball-milled, allow it to settle naturally to remove the surface liquid and obtain a moist solid precipitate. Then, place it in an oven and dry it at 80°C to obtain ball-milled biochar (labeled as QBC).

[0031] The performance of six materials—biochar (BC), pyrolytic manganese slag (MZ), biochar-manganese slag composite material (BM), waste manganese slag carbon-based composite material (QBM), ball-milled manganese slag prepared in Comparative Example 1 (QMZ), and ball-milled manganese slag-bought biochar prepared in Comparative Example 2 (QBC)—was tested and analyzed, as detailed below:

[0032] I. Determination of Physicochemical Properties

[0033] Six materials were analyzed for pH, conductivity, cation exchange capacity, particle size, and inorganic composition. pH and conductivity were measured using a pH meter (pHS-3E) and a conductivity meter (DDS-307) manufactured by Shanghai Leici Instruments Co., Ltd., respectively. Considering the low density of biochar, a suspension with a solid-liquid ratio of 1:10 was used for measurement. Surface charge was measured using a Zeta potential analyzer (Malvern Zetasizer 3600). 0.05 g of the prepared sample was weighed into a beaker and uniformly suspended in deionized water using a magnetic stirrer. Cation exchange capacity (CEC) was determined using the hexaamminecobalt trichloride leaching-spectrophotometric method. Particle size was measured using a particle size analyzer (Mastersizer-2000). For inorganic composition, 0.1 g of material was placed in a muffle furnace and calcined at 576℃ for 16 h. The remaining mass was then used to calculate the inorganic composition content. To ensure accuracy, four parallel samples were measured during each test, and this setup was maintained in subsequent experiments.

[0034] II. Leaching Determination and Ammonia Nitrogen Adsorption Experiment

[0035] The toxicity leaching of the research material was determined according to the Chinese Environmental Protection Standard HJ557-2010, "Leaching Method for Toxicity of Solid Waste". 2 g of material and 20 mL of deionized water were added to a 50 mL centrifuge tube at a solid-liquid ratio of 1:10. The mixture was shaken at 120 rpm for 8 hours, then allowed to stand for 16 hours before being filtered through a 0.45 μm filter to obtain the leachate sample for analysis. The contents of heavy metals such as manganese, copper, lead, zinc, nickel, arsenic, chromium, and cadmium in the leachate were determined using ICP-MS; simultaneously, the ammonia nitrogen concentration in the leachate sample was determined using sodium spectrophotometry.

[0036] In addition, to evaluate the adsorption of leaching elements by biochar and manganese slag during the composite preparation process, an adsorption experiment of ammonia nitrogen by biochar material was conducted. This experiment used ammonium chloride to prepare the ammonia nitrogen mother liquor. 0.10 g of BC and QBC were weighed into 50 mL centrifuge tubes, and then 20 mL of 20 mg·L⁻¹ manganese slag was injected. -1 An ammonium chloride solution was placed in a reciprocating shaking incubator and shaken at 25°C and 250 rpm for 24 hours. The solution was then centrifuged, filtered, and the concentration of ammonia nitrogen in the liquid was measured.

[0037] III. Adsorption Experiment of Sb(V) in Water

[0038] Potassium hexahydroxyantimonate was used to prepare an antimony solution to simulate antimony in water. 5 mL of concentrated hydrochloric acid was added and heated to dissolve the solution. 0.22 g of potassium hexahydroxyantimonate was dissolved in a beaker, diluted, and brought to a final volume of 100 mL in a volumetric flask to prepare a 1000 mg / L solution. -1 The antimony solution was diluted to 15 mg·L⁻¹. -1 Prepare the solution. Weigh 0.10 g of material into each 50 mL centrifuge tube, then add 20 mL of the pre-prepared potassium hexahydroxyantimonate solution. After tightening the cap, incubate at 25°C and 250 rpm for 24 hours with shaking and adsorption, then filter and analyze. All experiments were performed in quadruplicate.

[0039] IV. Data Processing

[0040] The content (%) of inorganic components is calculated using the following formula (1);

[0041] (1)

[0042] (Where M0(g) is the mass of the material before ignition, M1(g) is the mass of the crucible before ignition, and M2(g) is the mass of the crucible and the remaining material after ignition.)

[0043] The concentration of ammonia nitrogen was determined by sodium spectrophotometry, and the adsorption capacity was calculated using the following formula.

[0044] (2)

[0045] Where C0 (mg·L) -1 C is the initial concentration of the ammonia nitrogen working solution. e (mg·L) -1 ) is the remaining concentration of ammonia nitrogen after adsorption, M (g) is the amount of adsorbent, and V is the volume of the solution (L).

[0046] The Sb(V) concentration was determined using an atomic fluorescence spectrometer, and the adsorption capacity and removal rate were calculated according to formulas (3) and (4):

[0047] (3)

[0048] (4)

[0049] Where C0 (mg·L) -1 ) is the initial concentration of Sb(V), C e (mg·L) -1 ) is the concentration of Sb(V) at equilibrium, M(g) is the amount of adsorbent, and V is the volume of the solution (L); the removal efficiency is expressed as a percentage of Sb(V) (%R) and is calculated using the above equation.

[0050] V. Results Analysis

[0051] The physicochemical properties of the 6 materials are as follows Figure 1 As shown, biochar (BC), pyrolytic manganese slag (MZ), and biochar-manganese slag composite (BM) are all alkaline, with pH values ​​of 10.13, 8.71, and 9.17, respectively. Compared to the original materials, the average pH values ​​of ball-milled manganese slag-based biochar (QBC), waste manganese slag carbon-based composite (QBM), and ball-milled manganese slag (QMZ) are 9.35, 8.18, and 8.28, respectively. The pH values ​​of the materials after ball milling decreased slightly (P<0.05), specifically QBC (9.35), QBM (8.18), and QMZ (8.28). Similarly, the electrical conductivity of BC, BM, and MZ before ball milling decreased from 4.92, 5.73, and 5.79 mS / cm to 0.56, 2.84, and 2.08 mS / cm for QBC, QMZ, and QBM after ball milling. However, contrary to experimental expectations, ball milling increased the surface charge of the materials (P<0.05). The specific surface charges of BC, BM, and MZ increased from -23.88 mV, -8.2 mV, and -14.5 mV to QBC (-26.53 mV), QBM (-10.68 mV), and QMZ (-20.6 mV), respectively. Simultaneously, cation exchange capacity measurements also showed that ball milling increased the cation exchange capacity of BC, BM, and MZ from BC (8.52 cmol·kg⁻¹) to QBC (-26.53 mV), QBM (-10.68 mV), and QMZ (-20.6 mV), respectively. -1 ), BM (4.22 cmol·kg -1MZ (6.51 cmol·kg) -1 The levels were reduced to QBC (6.82 cmol·kg⁻¹). -1 QBM (3.40 cmol·kg) -1 ), QMZ (5.53 cmol·kg) -1 (P<0.05). Regarding the ash content in the materials, although there are significant differences in the composition of the original materials, with BC accounting for 16.91%, MZ has an inorganic component ratio of 91.72%, and BM's inorganic component ratio is in between. Since ball milling is a physical method, it has little effect on the inorganic component ratio, resulting in a slight decrease, but without significant difference. However, wet ball milling significantly reduced the average particle size of the studied materials (P<0.05). Compared with the original materials BC, MZ, and BM, the average particle sizes of the ball-milled materials QBC, QMZ, and QBM decreased by 72.4%, 86.6%, and 70.9%, respectively.

[0052] The raw material used in this invention, waste manganese slag, mainly contains Mn. 2+ Cr 3+ and NH 4+ Excessive levels of certain substances can easily pollute surrounding water bodies. For example... Figure 2 and Figure 3 As shown in the leaching determination study, the leaching liquids of MZ, BM, QMZ, and QBM showed that Mn in MZ before ball milling... 2+ and NH 4+ This significantly exceeds my country's "Wastewater Discharge Standard." This further confirms that waste manganese slag cannot be used directly without treatment. Furthermore, the Mn content in BM's leachate... 2+ The levels of NH4+ are near emission standards, posing a certain pollution risk, but... 4+ The levels are significantly lower than the "Wastewater Discharge Standard". Clearly, after mixing manganese slag and biochar, the biochar effectively reduces the amount of Mn in the manganese slag. 2+ and NH 4+ Adsorption (e.g.) Figure 4 As shown), it significantly reduced Mn in MZ. 2+ and NH 4+ The release of Mn was observed. However, simple biochar mixing still carries the potential risk of pollution from the adsorbent material. After ball milling, the leached elements in the three materials, QBC, QMZ, and QBM, all met emission standards. Clearly, wet ball milling further reduced the Mn content in the corresponding materials. 2+ and NH 4+ Leaching. As discussed earlier regarding the effect of ball milling on the pH of materials, BC, MZ, and BM release a large amount of Mn during the ball milling process. 2+ and NH 4+It dissolves in water and leaves the water during solid-liquid separation, thus reducing the Mn content in the adsorbent material after ball milling. 2+ and NH 4+ The leaching of Mn in the manganese slag can be reduced to some extent by combining biochar and manganese slag. 2+ and NH 4+ Leaching, while ball milling further reduces the amount of Mn in manganese slag and its composites. 2+ and NH 4+ The leaching process provides a safe guarantee for the resource utilization of manganese slag and the preparation of ball-milled biochar-manganese slag composite materials.

[0053] like Figure 5 As shown, comparison Figure 5The removal rates of BM and QBM indicate that mixing biochar with manganese slag does indeed improve the adsorption of Sb(V), and wet ball milling further enhances the removal and adsorption capacity of the biochar-manganese slag composite material (BM) for Sb(V). This is because manganese slag contains a large amount of iron-manganese oxides, which can complex with Sb(V), thus exhibiting a strong effect in removing Sb(V). The biochar-manganese slag composite material should show stronger adsorption performance for Sb(V) than biochar and pyrolytic manganese slag. However, because biochar has a strong alkalinity and a negatively charged surface, direct composite formation weakens the adsorption of antimony anions by manganese slag, showing that BM has worse adsorption performance than MZ. However, the waste manganese slag carbon-based composite material (QBM) obtained after ball milling shows a significant improvement in Sb(V) adsorption performance compared to ball-milled manganese slag (QMZ). The main reasons are as follows: First, wet ball milling washes away a large amount of alkaline substances from the biochar during the milling process and separates them from the material during solid-liquid separation, reducing the number of negative charges on the material surface. This weakens the electrostatic repulsion between the material and antimony anions, enhancing the complexation between Sb(V) and the material. Second, wet ball milling simultaneously reduces the cation exchange capacity of the material, decreasing the adsorption of cations by the QBM and increasing the contact probability between the material and antimony anions. Third, ball milling reduces the particle size, increases the internal and external specific surface area of ​​the material, and increases the exposure of micropores in the particles, thus increasing the number of Sb(V) adsorption sites. In addition, wet ball milling also alters the order of adsorption strength of the material. In the original materials, MZ contains more Sb(V) binding sites such as iron and manganese oxides, which is conducive to Sb(V) binding and has the highest removal efficiency. In the wet ball milling materials, QBC removes some surface negative charges through washing, and exposes more micropores and functional groups on the inner and outer surfaces, enhancing antimony adsorption. QBM, under the action of wet ball milling, has a large number of finer manganese slag particles attached to the surface and pores of biochar, forming a more stable manganese slag modified surface, and the number of antimony adsorption sites per unit mass increases significantly, thus exhibiting the best adsorption performance. Although the ball-milled biochar also achieves a relatively high removal rate and adsorption capacity for Sb(V), why is it necessary to use environmentally polluting waste manganese slag in this invention? On the one hand, it can reduce raw material costs, and on the other hand, it can treat waste manganese slag and protect the environment. Therefore, the method of preparing waste manganese slag carbon-based composite materials in this invention provides a way of resource utilization of manganese slag, and is expected to alleviate the problems of resource waste and environmental pollution caused by long-term stockpiling of manganese slag.

[0054] It should be noted that the mass ratio of biochar to pyrolytic manganese slag during ball milling in this invention was obtained through extensive experimental analysis based on the content of heavy metal pollutants in the waste manganese slag and the adsorption performance of biochar. The ultimate goal is to achieve the lowest cost and the highest Sb(V) adsorption. Therefore, the ratio was determined through trial and error, not by conventionally referring to any other technical solution. The experimental conditions for ball milling, including the combination of three sizes of mixed stainless steel grinding balls, the ratio of grinding balls to materials and water, and the milling rate and time, were obtained by the inventors through trial, analysis, and summarization. No related reports in this field have ever disclosed these technical features. Therefore, obtaining a composite material with Sb(V) adsorption capacity by wet ball milling of biochar and waste manganese slag is expected to be applied in the future for controlling antimony in soil and achieving environmentally friendly treatment of waste manganese slag.

[0055] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention in any way. Any simple modifications, alterations, and equivalent changes made to the above embodiments based on the inventive essence shall still fall within the protection scope of the present invention.

Claims

1. A method for preparing a waste manganese slag carbon-based composite material for controlling and removing antimony, characterized in that: The method comprises the following steps: mixing the ground biochar and pyrolysis manganese residue according to a mass ratio of 1:1, then placing them in a ball mill tank, adding deionized water which is not less than 6 times the total mass of the biochar and the electrolytic manganese residue, using three kinds of mixed stainless steel grinding balls with diameters of 15mm, 25mm and 35mm for ball milling, naturally precipitating the ball-milled mixture, removing the surface liquid to obtain a moist solid precipitate, then placing the moist solid precipitate in an oven for drying to obtain the waste manganese residue carbon-based composite material. ​ The mass ratio of the three kinds of stainless steel grinding balls with diameters of 15mm, 25mm and 35mm is 1:1:1, and the mass ratio of the total mass of the biochar and the electrolytic manganese residue to the mass of the mixed stainless steel grinding balls is 1:

20. The waste manganese residue is placed in a cracking furnace and burned at a high temperature of 550 DEG C for 2 hours to obtain the pyrolysis manganese residue, and the corn straw powder is ground and placed in the cracking furnace, pyrolyzed at a high temperature of 550 DEG C for 2 hours under nitrogen protection to obtain the biochar.

2. The preparation method of the waste manganese residue carbon-based composite material for controlling and restricting antimony according to claim 1, characterized in that: The ball milling speed is 150r / min, and the time is 8h.

3. The preparation method of the waste manganese residue carbon-based composite material for controlling and restricting antimony according to claim 1, characterized in that: The drying time is 80 DEG C.

4. The preparation method of the waste manganese residue carbon-based composite material for controlling and restricting antimony according to claim 1, characterized in that: The biochar and the pyrolysis manganese residue are ground to 100 mesh.

5. Use of the antimony controlled waste manganese residue carbon-based composite material prepared according to the method of any one of claims 1-4, characterized in that: The waste manganese residue carbon-based composite material is used for controlling and inhibiting antimony pollution in soil. The waste manganese residue carbon-based composite material is used for controlling and inhibiting antimony pollution in soil.

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