Electrochemical in-situ generation of Schottky minerals and simultaneous removal of Sb(III) and Sb(V)

Abstract

The invention discloses a method for electrochemically generating Schwartzite in situ and removing Sb (III) and Sb (V) simultaneously, the method comprising the steps: acid mine wastewater is placed in a container, and an anode electrode and a cathode electrode are inserted to form a double electrode electrolytic cell; electrochemical reaction is carried out by constant current method, and the precipitate generated is filtered; wherein, the content of Sb (III) in acid mine wastewater is 0.1 100 mg / L; the content of Sb (V) in acid mine wastewater is 0.1 150 mg / L; the anode electrode is any one of a coated titanium-based electrode, a coated titanium-based electrode, a Pt electrode or a graphite electrode, and the cathode electrode is any one of a 304 stainless steel electrode or a Pt electrode. The method of the present invention realizes the common removal of Sb (III) and Sb (V) in water by electrochemical means, and the method has remarkable removal effect, and no complicated adsorbent preparation process, no addition of exogenous agents, and process is simple, easy to operate.

Description

Technical Field

[0001] The present invention belongs to the technical field of heavy metal removal, and in particular relates to a method for electrochemically generating in-situ Schreiberite and simultaneously removing Sb(III) and Sb(V). Background Art

[0002] Antimony (Sb) is a toxic metalloid pollutant from Group 15 of the periodic table. It is widely used in the manufacturing of textiles, flame retardants for plastics, ceramics, glassware, brake pads, and electronic components. Antimony is a metalloid that exists naturally in the forms of Sb(III) and Sb(V). my country has the world's largest antimony reserves and is the world's largest producer of antimony and its compounds. During the mining and smelting process, the dissolution, weathering, and oxidation of sulfur- and antimony-containing minerals generate large amounts of acid mine drainage (AMD) containing Sb(III) and its oxidation product, Sb(V).

[0003] In the existing technology, the antimony pollution treatment technology mainly relies on the adsorption method. However, the adsorption method has the problems of complex preparation method of adsorption materials, long hydrothermal reaction time, high cost, harsh reaction conditions, etc., which limit its application in the in-situ remediation of antimony pollution in AMD. Schmidt mineral is a secondary iron mineral naturally generated in AMD, with a large specific surface area and exchangeable sulfate, showing a strong fixation ability for oxygen-containing anions including Sb. In nature, light and microbial Fe(II) oxidation can promote the formation of Schmidt mineral, and fix pollutants such as Sb in the mineral structure or on the surface through co-precipitation and adsorption during the mineralization process, thereby reducing the mobility of pollutants. However, Schmidt mineral naturally formed in the AMD environment has problems such as low mineralization efficiency, resulting in incomplete removal of pollutants in the overlying water. In order to better utilize the advantage of Schmidt mineral being suitable for acidic environment, researchers have artificially synthesized Schmidt mineral as an adsorbent to treat acidic mine wastewater. Although it can play a considerable role in removing Sb, the addition of exogenous Schmidt mineral introduces new Fe and SO4 into the environment. 2- The pollution sources increase the difficulty of comprehensive environmental management in mining areas.

[0004] Chinese patent application CN202010142704.9 discloses a method for the rapid electrochemical deposition synthesis of Schroeder mineral. The synthesized Schroeder mineral has high specific surface area, uniform particle size, a typical sea urchin spherical microstructure, and abundant surface whiskers. However, this method solves the technical problem of obtaining Schroeder mineral with a high degree of crystallinity. The method is not very effective in fixing Sb during the mineralization process, resulting in a low removal rate.

[0005] In summary, utilizing the substances contained in AMD to increase the mineralization rate of Schroeder's mineralization can improve the Sb removal efficiency of overlying water while avoiding the introduction of new pollution sources. Therefore, developing a method for the controlled synthesis of Schroeder's mineralization is of great significance for the in-situ treatment of antimony contamination in acidic wastewater. Summary of the Invention

[0006] Based on this, the present invention provides a method for electrochemically generating in situ Schreiberite and simultaneously removing Sb(III) and Sb(V), the method comprising the following steps:

[0007] (1) Place acid mine drainage in a container and insert an anode electrode and a cathode electrode to form a two-electrode electrolytic cell;

[0008] (2) Under magnetic stirring conditions, the electrochemical reaction is carried out by constant current method, and the generated precipitate is filtered;

[0009] Wherein, in step (1), the content of Sb (III) in the acid mine wastewater is 0.1-100 mg / L; the content of Sb (V) in the acid mine wastewater is 0.1-150 mg / L; the anode electrode is Coated titanium-based electrodes, The cathode electrode is any one of a coated titanium-based electrode, a Pt electrode or a graphite electrode, and the cathode electrode is any one of a 304 stainless steel electrode or a Pt electrode.

[0010] The principle of the electrochemical reaction of the present invention is to promote the oxidation of Sb(III) and Fe(II) in acid mine wastewater at the anode by electrochemical means and adopt constant current method, and promote the reduction of oxygen at the cathode to react with OH - The increase of pH promotes the hydrolysis reaction between Fe(III) generated at the anode and the original Fe(III) in the acid mine wastewater. 2- Under the regulation of the electrochemical oxidation reaction, Schreiber mineral is generated, and during the precipitation process, Sb(V) originally contained in the acidic mine wastewater and Sb(III) produced by oxidation are entrained into the Schreiber mineral lattice to form a co-precipitation. The generated Schreiber mineral further fixes the remaining Sb(V) in the solution through adsorption. Under the combined action of electrochemical oxidation, co-precipitation and adsorption, the Sb(III) and Sb(V) in the aqueous phase are jointly removed. The electrochemical method of the present invention increases the design of hydroxyl-rich sites, significantly increases the fixation ability of Schreiber mineral for Sb(III) and Sb(V), and improves the removal rate.

[0011] In addition, the method of the present invention can also significantly reduce Fe, SO4 2- and H + content, realizing in-situ purification of wastewater.

[0012] In step (2) of the present invention, the rate of magnetic stirring is preferably 60-100 rpm.

[0013] According to the method for electrochemical in-situ generation of Schottky mineral and simultaneous removal of Sb(III) and Sb(V) according to claim 1, preferably, in step (1), the anode electrode is The coated titanium-based electrode and the cathode electrode are 304 stainless steel electrodes.

[0014] The method for electrochemical in situ generation of Schreiberite and simultaneous removal of Sb(III) and Sb(V) according to claim 1, preferably, the electrochemical reaction selects the chronopotentiometry mode, and the cathode current is set to 0 mA, the anode current is set to 180-220 mA, the cathode time is set to 0 s, and the anode time is set to 7200-10800 s.

[0015] In the method for electrochemical in-situ generation of Schottky minerals and simultaneous removal of Sb(III) and Sb(V) according to claim 1, preferably, in step (2), the anodic time is 3600-9000 s. Using the method of the present invention, after the anodic time reaches 3600 s, the content of Sb(III) and Sb(V) in the wastewater is already very low, and further electrochemical reaction is performed, and the content of Sb(III) and Sb(V) in the wastewater decreases slowly; and after 9000 s, the content of Sb(III) and Sb(V) in the wastewater decreases almost insignificantly.

[0016] According to the method for electrochemical in-situ generation of Schreiberite and simultaneous removal of Sb(III) and Sb(V) according to claim 1, preferably, the content of Sb(III) in the acid mine wastewater is 1-50 mg / L.

[0017] According to the method for electrochemical in-situ generation of Schroederite and simultaneous removal of Sb(III) and Sb(V) according to claim 1, preferably, in step (1), the content of Sb(V) in the acid mine wastewater is 1-100 mg / L.

[0018] As a preferred embodiment of the present invention, the Sb (III) content in the acidic mine drainage water is 1-20 mg / L, and the Sb (V) content in the acidic mine drainage water is 1-50 mg / L. As a more preferred embodiment of the present invention, the Sb (III) content in the acidic mine drainage water is 1-10 mg / L, and the Sb (V) content in the acidic mine drainage water is 1-20 mg / L. The electrochemical method of the present invention is more suitable for removing Sb (III) and Sb (V) in acidic mine drainage water within the above-mentioned concentration ranges. It can achieve an Sb (III) removal rate of 100% and a total Sb removal rate of over 93%.

[0019] According to the method for electrochemical in-situ generation of Schroederite and simultaneous removal of Sb(III) and Sb(V) according to claim 1, preferably, the anode electrode and the cathode electrode are treated by the following steps before use:

[0020] Soak the anode electrode in 5%-15% hydrochloric acid solution for 20-40 minutes to remove surface oxides, then rinse with deionized water and finally blow dry with inert gas;

[0021] The cathode electrode was polished with 1000-1500 grit sandpaper to remove the passivation layer, and then ultrasonically cleaned with acetone, ethanol, and deionized water in sequence, and finally dried with inert gas.

[0022] According to the method for electrochemical in-situ generation of Schroederite and simultaneous removal of Sb(III) and Sb(V) according to claim 1, preferably, in step (1), the pH value of the acid mine drainage is 2-4.

[0023] According to the method for electrochemical in-situ generation of Schroederite and simultaneous removal of Sb(III) and Sb(V) according to claim 1, preferably, in step (1), the total Fe content in the acid mine drainage water is 200-1000 mg / L, and the Fe(II) content is 80-150 mg / L. Further preferably, the total Fe content in the acid mine drainage water is 500-800 mg / L, and the Fe(II) content is 100-130 mg / L.

[0024] The method for electrochemical in-situ generation of Schroederite and simultaneous removal of Sb(III) and Sb(V) according to claim 1, preferably, in step (1), the content of Sb(III) in the acid mine wastewater is 1-10 mg / L; the content of Sb(V) is 1-20 mg / L; SO4 2- The content of the above components is 1000-2000 mg / L. The method of the present invention is used to treat the wastewater, which can not only increase the Sb removal rate to more than 93%, but also improve the SO4 2- In-situ purification effect.

[0025] As a specific embodiment of the present invention, the content of Sb (III) in the acid mine wastewater is 1-10 mg / L; the content of Sb (V) is 1-20 mg / L; SO4 2- The content of Sb(III) and Sb(V) is 1000-2000 mg / L; the total Fe content is 500-800 mg / L, and the Fe(II) content is 100-130 mg / L. Treating wastewater within the above range can not only effectively remove Sb(III) and Sb(V), but also reduce the Fe and SO42- and H + Content, especially SO4 2- The removal effect is more significant. Beneficial effects

[0026] Compared with the prior art, the present invention has the following beneficial effects:

[0027] The method of the present invention uses electrochemical means and a constant current method to generate Schrödinger mineral in acidic mine wastewater without adding exogenous reagents. During the precipitation process, Sb(III) and Sb(V) are entrained into the Schrödinger mineral lattice to form a co-precipitate. The generated Schrödinger mineral further fixes the remaining Sb(III) and Sb(V) in the solution through adsorption. Under the combined action of coprecipitation and adsorption, Sb(III) and Sb(V) in the aqueous phase are jointly removed. The method has a significant removal effect, does not require a complex adsorbent preparation process, does not require the addition of exogenous reagents, and has a simple process and is easy to operate.

[0028] In addition, the method of the present invention also reduces Fe, SO4 2- and H + content, realizing in-situ purification of wastewater. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 This is a working principle diagram of a method for electrochemically generating in situ Schreiberite and simultaneously removing Sb(III) and Sb(V) according to the present invention.

[0030] Figures 2(a), 2(b), 2(c), 2(d) and 2(e) are all graphs showing the change of the main components of the electrolyte over time in the constant current electrochemical reaction in acidic mine wastewater with different Sb (III) and Sb (V) concentrations in a method for electrochemical in-situ generation of Schreiberite and simultaneous removal of Sb (III) and Sb (V) according to the present invention. Figure 2(a) shows the change of the content of Fe (II) over time in Examples 1-3; Figure 2(b) shows the change of the content of SO4 in Examples 1-3. 2- Figure 2 (c) is a graph showing the changes in the content of Sb(III) and Sb(V) over time in Example 1; Figure 2 (d) is a graph showing the changes in the content of Sb(III) and Sb(V) over time in Example 2; Figure 2 (e) is a graph showing the changes in the content of Sb(III) and Sb(V) over time in Example 3.

[0031] Figure 3This is a method for the electrochemical in situ generation of Schreiberite and the simultaneous removal of Sb(III) and Sb(V) according to the present invention. The X-ray diffraction pattern of the solid phase particles obtained after a constant current electrochemical reaction for 3 hours in the acidic mine wastewater of Example 4 is shown. The symbol marks the characteristic peak of Schreiberite. DETAILED DESCRIPTION

[0032] To facilitate understanding of the present invention, the present invention will be described more fully below in conjunction with specific embodiments. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the content of the present invention more thoroughly and comprehensively understood.

[0033] In the present invention, the MMO anode (i.e. The MMO anode and 304 stainless steel cathode were purchased from Suzhou Shuertai Industrial Technology Co., Ltd., with a size of 30 mm × 30 mm. The following method was used to treat the MMO anode and 304 stainless steel cathode:

[0034] Treatment of MMO anode: First, soak the MMO electrode with a size of 30 mm × 30 mm in 10% hydrochloric acid solution for 30 minutes for pickling to remove surface oxides, then rinse it with deionized water, and finally blow dry with nitrogen.

[0035] Treatment of 304 stainless steel cathode: A 304 stainless steel electrode with a size of 30 mm × 30 mm was polished with 1500 grit sandpaper to remove the passivation layer, and then ultrasonically cleaned with acetone, ethanol, and deionized water in sequence, and finally dried with nitrogen.

[0036] Preparation of Sb(III) stock solution: Accurately weigh 0.0729 g of antimony trioxide (Sb2O3) using an analytical balance (precision 0.0001 g) and dissolve it in 33.3 mL of a 1:1 (v:v) hydrochloric acid solution. Dose the volume to 100 mL to obtain a 5 mM Sb(III) stock solution. Pour the stock solution into a reagent bottle and store at 4°C in the dark.

[0037] Preparation of Sb(V) stock solution: Use an analytical balance (precision 0.0001 g) to accurately weigh 0.1315 g of potassium pyroantimonate (KSb(OH)6), stir and dissolve it in 50 mL of deionized water preheated to 60°C. After cooling to room temperature, transfer it to a 100 mL volumetric flask. Wash the beaker three times with pure water, add the washings to the volumetric flask, and adjust the volume to 100 mL to obtain a Sb(V) stock solution with a concentration of 5 mM. Pour this stock solution into a reagent bottle and store at 4°C.

[0038] Preparation of acid mine drainage: 2.78 g of ferrous sulfate heptahydrate (FeSO4·7H2O), 1.42 g of anhydrous sodium sulfate (Na2SO4), a certain amount of Sb(III) stock solution, and a certain amount of Sb(V) stock solution were dissolved in deionized water and the volume was adjusted to 1 L. The pH of the solution was adjusted to 3.0 with dilute sulfuric acid and sodium hydroxide to obtain acid mine drainage containing different Sb(III) and Sb(V) concentrations.

[0039] Determination method of ingredient content:

[0040] The suspension after the electrochemical reaction is filtered through a microporous filter membrane to obtain a filtrate and a solid precipitate. The solid precipitate is freeze-dried and then ground through a 200-mesh sieve to obtain solid phase particles.

[0041] The contents of Sb(III) and total Sb in the filtrate were determined by ICP-AFS-HPLC, and the content of Sb(V) was obtained by subtracting the total Sb content from the Sb(III) content.

[0042] The total Fe and Fe(II) contents in the filtrate were determined by ultraviolet-visible spectrophotometry (UV-Vis);

[0043] Determination of SO4 in the filtrate by anion chromatography (IC) 2- content;

[0044] The solid phase particles were measured by X-ray diffraction spectrometer (XRD) to determine the composition of the solid phase particles.

[0045] The removal rates of Sb(III) and Sb(V) were obtained by the following formula:

[0046] Removal rate = (C0-C t ) / C0×100%,

[0047] Where C0 represents the initial Sb(III), Sb(V) or total Sb concentration;

[0048] C t Represents the concentration of Sb(III), Sb(V) or total Sb when the reaction reaches time t. Example 1

[0049] A method of electrochemically generating in-situ Schroederite and simultaneously removing Sb(III) and Sb(V) in this embodiment includes the following steps:

[0050] (1) 300 mL of acidic mine wastewater solution containing 1.2 mg / L Sb(III) and 1.22 mg / L Sb(V) was added to a 500 mL cylindrical glass electrolytic cell. A magnetron was placed in the electrolytic cell. During the reaction, the reaction was stirred at 80 rpm. The treated MMO anode and 304 stainless steel cathode were inserted into the electrolytic cell.

[0051] (2) Connect the computer to the electrochemical workstation (CHI 660E, Shanghai Chenhua) and use the constant current method to perform the electrochemical reaction. The specific operation is: select the chronopotentiometry mode, set the cathode current to 0 mA, the anode current to 200 mA, the cathode time to 0 s, and the anode time to 10800 s.

[0052] At the electrochemical reaction time of 0, 5, 10, 30, 60, 90, 120, 150, and 180 min, 3 mL of samples were taken through a 0.22 μm needle filter membrane, and the Fe(II) content in the filtrate was determined by UV-Vis, and the SO4 content in the filtrate was determined by IC method. 2- The content of Sb(III) and total Sb in the filtrate was determined by ICP-AFS-HPLC, and the content of Sb(V) was obtained by subtracting the total Sb content from the Sb(III) content. The changes of Sb(III) and Sb(V) with time during the reaction are shown in Figure 2(c).

[0053] Removal efficiency of Sb(III) and Sb(V): After 3 h of reaction, the contents of Sb(III) and Sb(V) in the solution were 0.00 mg / L and 0.029 mg / L, respectively. The removal efficiency of Sb(III) was (1.2-0.00) / 1.2×100% = 100%, the removal efficiency of Sb(V) was (1.2-0.029) / 1.2×100% = 97.6%, and the total Sb removal efficiency was [(1.2+1.2)-(0.00+0.029)] / (1.2+1.2)×100% = 98.8%. Example 2

[0054] A method of electrochemically generating in-situ Schroederite and simultaneously removing Sb(III) and Sb(V) in this embodiment includes the following steps:

[0055] (1) 300 mL of acidic mine wastewater solution containing 6.1 mg / L Sb(III) and 12.2 mg / L Sb(V) was added to a 500 mL cylindrical glass electrolytic cell. A magnetron was placed in the electrolytic cell. During the reaction, the reaction was stirred at 80 rpm. The treated MMO anode and 304 stainless steel cathode were inserted into the electrolytic cell.

[0056] (2) Connect the computer to the electrochemical workstation (CHI 660E, Shanghai Chenhua) and use the constant current method to perform the electrochemical reaction. The specific operation is: select the chronopotentiometry mode, set the cathode current to 0 mA, the anode current to 200 mA, the cathode time to 0 s, and the anode time to 10800 s.

[0057] At the electrochemical reaction time of 0, 5, 10, 30, 60, 90, 120, 150, and 180 min, 3 mL of samples were taken through a 0.22 μm needle filter membrane, and the Fe(II) content in the filtrate was determined by UV-Vis, and the SO4 content in the filtrate was determined by IC method. 2- The content of Sb(III) and total Sb in the filtrate was determined by ICP-AFS-HPLC, and the content of Sb(V) was obtained by subtracting the total Sb content from the Sb(III) content. The changes of Sb(III) and Sb(V) with time during the reaction are shown in Figure 2(d).

[0058] Removal efficiency of Sb(III) and Sb(V): After 3 h of reaction, the contents of Sb(III) and Sb(V) in the solution were 0.00 mg / L and 0.63 mg / L, respectively. The removal efficiency of Sb(III) was (6.1-0.00) / 6.1×100% = 100%, and the removal efficiency of Sb(V) was (12.2-0.63) / 12.2×100% = 94.8%. The total Sb removal efficiency was [(6.1+12.2)-(0.00+0.63)] / (6.1+12.2)×100% = 96.6%. Example 3

[0059] A method of electrochemically generating in-situ Schroederite and simultaneously removing Sb(III) and Sb(V) in this embodiment includes the following steps:

[0060] (1) 300 mL of acidic mine wastewater solution containing 24.4 mg / L Sb(III) and 61.0 mg / L Sb(V) was added to a 500 mL cylindrical glass electrolytic cell. A magnetron was placed in the electrolytic cell. During the reaction, the reaction was stirred at 80 rpm. The treated MMO anode and 304 stainless steel cathode were inserted into the electrolytic cell.

[0061] (2) Connect the computer to the electrochemical workstation (CHI 660E, Shanghai Chenhua) and use the constant current method to perform the electrochemical reaction. The specific operation is: select the chronopotentiometry mode, set the cathode current to 0 mA, the anode current to 200 mA, the cathode time to 0 s, and the anode time to 10800 s.

[0062] At the electrochemical reaction time of 0, 5, 10, 30, 60, 90, 120, 150, and 180 min, 3 mL of samples were taken through a 0.22 μm needle filter membrane, and the Fe(II) content in the filtrate was determined by UV-Vis, and the SO4 content in the filtrate was determined by IC method. 2- The content of Sb(III) and total Sb in the filtrate was determined by ICP-AFS-HPLC, and the content of Sb(V) was obtained by subtracting the total Sb content from the Sb(III) content. The changes of Sb(III) and Sb(V) with time during the reaction are shown in Figure 2(e).

[0063] Removal efficiency of Sb(III) and Sb(V): After 3 h of reaction, the contents of Sb(III) and Sb(V) in the solution were 0.00 mg / L and 6.63 mg / L, respectively. The removal efficiency of Sb(III) was (24.4-0.00) / 24.4×100% = 100%, and the removal efficiency of Sb(V) was (61.0-6.63) / 61.0×100% = 89.1%. The total Sb removal efficiency was [(24.4+61.0)-(0.00+6.63)] / (24.4+61.0)×100% = 92.2%. Example 4

[0064] The present embodiment provides a method for electrochemically generating in situ Schmidt minerals and simultaneously removing Sb(III) and Sb(V). Except for the use of different acid mine wastewater, the other steps are the same as those of Example 1. In this embodiment, the acid mine wastewater is obtained by filtering the surface runoff from the downstream of the Xikuangshan mining area in Hunan Province through a 0.22 μm filter membrane. The total Fe and Fe(II) contents in the wastewater filtrate are determined by UV-Vis method; the Sb(III) and total Sb contents in the wastewater filtrate are determined by ICP-AFS-HPLC; and the SO4 in the wastewater filtrate is determined by IC. 2- The main components and contents of the wastewater filtrate are: 582.1 mg / L total Fe, 104.6 mg / L Fe(II), 1749.3 mg / L SO4 2- , 3.9 mg / L Sb(III), 17.3 mg / L Sb(V).

[0065] After the electrochemical reaction in Example 1 was completed, the resulting suspension was filtered through a 0.22 μm filter membrane, and the contents of Sb(III) and total Sb in the filtrate were determined by ICP-AFS-HPLC. Calculations showed that after 3 h of reaction, the contents of Sb(III) and Sb(V) in the filtrate were 0.00 mg / L and 1.49 mg / L, respectively, and the removal rates of Sb(III), Sb(V), and total Sb were 100%, 91.4%, and 93.0%, respectively. The solid obtained by filtration was freeze-dried for 48 h, then ground and passed through a 200-mesh sieve. The solid phase composition was detected by XRD, and the XRD results were as follows: Figure 3 As shown, it is consistent with the characteristics of Schmidt mineral.

[0066] The technical features of the above-mentioned embodiments can be combined arbitrarily. In order to make the description concise, not all possible combinations of the technical features in the above-mentioned embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0067] The above-described embodiments merely illustrate several implementations of the present invention, and while their descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the patent. It should be noted that a person skilled in the art would be able to make numerous variations and improvements without departing from the spirit of the present invention, all of which fall within the scope of protection of the present invention. Therefore, the scope of protection of the patent for this invention shall be determined by the appended claims.

Claims

1. A method for electrochemically generating in situ Schreiberite and simultaneously removing Sb(III) and Sb(V), characterized in that: The method comprises the following steps: (1) Place acid mine drainage in a container and insert an anode electrode and a cathode electrode to form a two-electrode electrolytic cell; (2) Under magnetic stirring conditions, the electrochemical reaction is carried out by constant current method, and the generated precipitate is filtered; Wherein, in step (1), the total Fe content in the acid mine wastewater is 200-1000 mg / L, the Fe(II) content is 80-150 mg / L; the Sb(III) content in the acid mine wastewater is 1-10 mg / L; the Sb(V) content is 1-20 mg / L; SO4 2- The content of is 1000-2000 mg / L; the anode electrode is any one of a RuO2-IrO2 coated titanium-based electrode, a Ta2O5-IrO2 coated titanium-based electrode, a Pt electrode or a graphite electrode; the cathode electrode is any one of a 304 stainless steel electrode or a Pt electrode; the pH value of the acid mine wastewater is 2-4; In step (2), the chronopotentiometry mode was selected for the electrochemical reaction, and the cathode current was set to 0 mA, the anode current was set to 180-220 mA, the cathode time was set to 0 s, and the anode time was set to 7200-10800 s.

2. The method for electrochemically generating in situ Schroederite and simultaneously removing Sb(III) and Sb(V) according to claim 1, characterized in that: In step (1), the anode electrode is a RuO2-IrO2 coated titanium-based electrode, and the cathode electrode is a 304 stainless steel electrode.

3. The method for electrochemically generating in situ Schreiberite and simultaneously removing Sb(III) and Sb(V) according to claim 1, characterized in that: In step (1), the anode electrode and the cathode electrode are processed by the following steps before use: Soak the anode electrode in 5%-15% hydrochloric acid solution for 20-40 minutes to remove surface oxides, then rinse with deionized water and finally blow dry with inert gas; The cathode electrode was polished with 1000-1500 grit sandpaper to remove the passivation layer, and then ultrasonically cleaned with acetone, ethanol, and deionized water in sequence, and finally dried with inert gas.

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