Antimony hydrometallurgical process coupled with sulfur ion oxidation reactions

Abstract

The present application belongs to the field of hydrometallurgy, and particularly relates to a method for hydrometallurgy of antimony coupled with oxidation of sulfur ions, wherein antimony concentrate is leached in a leaching agent containing water-soluble sulfide A and base A to obtain an antimony-containing leaching solution; the antimony-containing leaching solution is subjected to electrolytic treatment in an electrolytic cell; the electrolytic cell comprises a container and a cationic diaphragm separating the container into an anode chamber and a cathode chamber; a cathode is arranged in the cathode chamber, and a composite anode with a sulfur ion oxidation catalyst is arranged in the anode chamber; during electrolysis, the antimony-containing leaching solution is used as electrolyte A and placed in the cathode chamber, and a solution containing water-soluble sulfide B and base B is used as electrolyte B and placed in the anode chamber, and then the anode and the cathode are electrically connected for electrolysis, so that antimony is deposited in the cathode chamber to form antimony, and in the process, sulfur ions are oxidized in the anode chamber. The method can improve the yield and purity of antimony, and can also effectively reduce energy consumption and consumption of anode base.

Description

Technical Field

[0001] The present invention belongs to the field of metallurgy and chemical industry, and in particular to the field of antimony hydrometallurgy. Background Art

[0002] Antimony is a key metallic material widely used in flame retardants, photovoltaic glass, lead-acid batteries, polyester catalysts, and alloy manufacturing. Antimony occurs primarily in nature as stibnite (Sb2S3), with a smaller amount occurring as antimony sinter (Sb2O3). Existing methods for producing metallic antimony can be categorized as pyrometallurgical and hydrometallurgical. Currently, the industry primarily utilizes the "blast furnace volatilization-reverberatory furnace reduction" process to produce metallic antimony. However, this process is energy-intensive and is accompanied by the emission of large amounts of low-concentration SO2 flue gas, making antimony smelting a significant contributor to environmental concerns.

[0003] Compared to pyrometallurgical antimony smelting, hydrometallurgical antimony smelting technology has attracted much attention due to its environmental advantages. Based on the differences in leaching systems, hydrometallurgical antimony smelting processes can be divided into acidic leaching processes and alkaline leaching processes. Acidic leaching processes, represented by chloride leaching-electrodeposition, have high requirements for equipment corrosion protection, and the leachate composition is complex and difficult to remove impurities, which is not conducive to continuous production and industrial application. Therefore, the existing technology tends to adopt sodium sulfide leaching-sodium thioantimonite solution electrodeposition (sodium sulfide leaching-electrodeposition). For example, Chinese patent document with publication number CN107641818A discloses a process for producing raw antimony, which comprises the following steps: flotation and leaching of an antimony ore containing 3% to 5% to obtain an antimony-containing leachate, and then using the antimony-containing leachate to produce raw antimony using a diaphragm-free electrodeposition method.

[0004] For example, Chinese patent document CN105063354A discloses a cascade recovery method for refractory gold ore containing arsenic and antimony. The method specifically describes adding sodium sulfide to the gold ore under alkaline conditions to leach antimony; the leachate is then electrolytically deposited to obtain cathode antimony liquid.

[0005] In summary, the existing technology reports some schemes for preparing antimony metal by electrolytic deposition of antimony sulfide and alkaline leaching solution, but the anode of the existing scheme will preferentially undergo oxygen evolution reaction (4OH - =O2+4e - +2H2O), which will increase the consumption of alkali, significantly increase the electricity and preparation costs. Not only that, the effect and efficiency of cathode antimony precipitation also need to be improved. Summary of the Invention

[0006] In response to the problems of the existing technology, the present invention provides an antimony hydrometallurgical method that couples sulfide ion oxidation reaction, aiming to provide a new antimony hydrometallurgical method that couples sulfide ion oxidation and antimony reduction to reduce costs and increase efficiency.

[0007] In the prior art, antimony concentrate is usually leached in the presence of sulfide and alkali, and the high-alkali leaching system is directly electrolyzed, and the electrolysis method is basically a diaphragm-free electrolysis method. In this electrolysis method, antimony is precipitated at the cathode, but the dominant reaction at the anode is oxygen evolution. This consumes a lot of electricity, and the antimony produced is difficult to meet the high-demand application scenarios. To address this problem, the present invention innovatively proposes the following new processing ideas, specifically:

[0008] The invention relates to an antimony hydrometallurgical method coupled with a sulfide ion oxidation reaction, wherein antimony concentrate is leached in a leaching agent containing a water-soluble sulfide A and an alkali A to produce an antimony-containing leachate; and the antimony-containing leachate is electrolytically treated in an electrolytic cell.

[0009] The electrolytic cell comprises a container and a cationic diaphragm that separates the container into an anode chamber and a cathode chamber; the cathode chamber is provided with a cathode, and the anode chamber is provided with an anode compounded with a sulfur ion oxidation catalyst;

[0010] During the electrolysis process, the antimony-containing leachate is used as electrolyte A and placed in the cathode chamber, and a solution containing water-soluble sulfide B and alkali B is used as electrolyte B and placed in the anode chamber. The anode and cathode are then conductively connected for electrolysis, so that antimony is deposited in the cathode chamber to form antimony. During this process, sulfur ions undergo an oxidation reaction in the anode chamber.

[0011] The present invention innovatively electrolyzes the antimony leachate in an electrolytic cell separated by a cationic membrane, and jointly controls the anode, electrolytes A, and electrolyte B. This allows for synergy, enabling electroreduction of antimony ions at the cathode and selective oxidation of sulfur ions at the anode. The method of the present invention couples antimony reduction and sulfur ion oxidation, and achieves unidirectional movement of active ions. The method of the present invention achieves efficient antimony conversion, improves antimony yield and purity, and effectively reduces energy consumption and anode alkali consumption.

[0012] In the present invention, the water-soluble sulfide A in the leaching agent is at least one of sodium sulfide and potassium sulfide.

[0013] The base A includes at least one of sodium hydroxide and potassium hydroxide.

[0014] In the leaching agent, the concentration of the water-soluble sulfide A is 20-80 g / L, and the concentration of the alkali A is 10-160 g / L. Furthermore, the concentration of the water-soluble sulfide A is 45-65 g / L, and the concentration of the alkali A is 20-35 g / L.

[0015] In the present invention, the temperature of the leaching process is 30-150° C., for example, 55-75° C.; the liquid-to-solid ratio in the leaching stage is 1-10 mL / g, for example, 3-5 mL / g;

[0016] The leaching time can be reasonably adjusted as needed, for example, 0.5 to 5 hours, and further 0.5 to 1 hour.

[0017] In the present invention, the cathode may be a conventional conductive cathode, such as graphite, a conductive metal plate (such as a single conductive metal plate) or a conductive alloy plate (conductive alloy plate, such as a steel plate).

[0018] In the present invention, known sulfur ion oxidation catalysts can be compounded in the anode of the present invention to achieve selective oxidation of sulfur ions in the anode chamber, and based on this, coupling of sulfur ion oxidation and antimony reduction is achieved.

[0019] In this invention, optimizing and controlling the anode catalytic material is expected to further improve the coupling effect between sulfur ion anodic oxidation and antimony cathode reduction. Preferably, the sulfur ion oxidation catalyst in the anode comprises cobalt ferrite and / or modified cobalt ferrite; the modified cobalt ferrite is cobalt ferrite modified with boron (B) and / or phosphorus (P). This preferred material facilitates integration with the inventive process, further enhancing the coupling effect between sulfur oxidation and antimony reduction.

[0020] In the present invention, the modified cobalt ferrite preparation method is, for example, to prepare the modified cobalt ferrite by heat-treating a material containing an iron source, a cobalt source, and a modification source (boron source and / or phosphorus source) to form nuclei. The nucleation temperature is, for example, 300-800°C.

[0021] In the present invention, the use of an anode with a preferred catalyst can further improve the coupling effect of sulfur ion oxidation and antimony reduction, and improve the yield, purity and quality of antimony.

[0022] Preferably, the anode is a self-supporting electrode composited with a sulfur ion oxidation catalyst, and its preparation steps are: a first-stage reaction of an iron substrate and a cobalt source, followed by a second-stage reaction with a borohydride and an alkali, and then a phosphating reaction.

[0023] The present invention's research shows that the anode prepared by the preferred process, combined with the process of the present invention, can further enhance the coupling effect of sulfur oxidation and antimony reduction, and help to further improve the yield, purity and quality of antimony.

[0024] In the present invention, the iron substrate is an iron sheet, foamed iron, an iron alloy sheet or foamed iron alloy;

[0025] The cobalt source is a water-soluble cobalt salt.

[0026] The weight ratio of the iron substrate to the cobalt element in the cobalt source is 1:0.005-0.1, preferably 1:0.01-0.03.

[0027] The temperature of the first stage reaction can be 50~100℃.

[0028] The first stage reaction time can be 10 to 60 hours, and further can be 20 to 50 hours.

[0029] The borohydride is at least one of sodium borohydride, potassium borohydride, and ammonium borohydride;

[0030] The base is an alkali metal hydroxide.

[0031] In the present invention, the molar ratio of the cobalt source, the borohydride, and the base is 1:5-20:5-20; further, it can be 1:7-12:7-12.

[0032] The temperature of the second stage reaction can be 5-45°C; further can be 20-35°C.

[0033] The second reaction period can be 2 to 10 hours, and further can be 5 to 9 hours.

[0034] The phosphorus source for the phosphating reaction includes a solid, liquid, or gaseous phosphorus-containing raw material. The solid phosphorus-containing raw material may be, for example, at least one of sodium phosphate, ammonium phosphate, potassium phosphate, potassium hydrogen phosphate, and sodium hydrogen phosphate. The liquid phosphorus-containing raw material may be, for example, phosphoric acid. The gaseous phosphorus-containing raw material may be, for example, PH3.

[0035] The molar ratio of P in the phosphorus source to cobalt in the cobalt source is 0.01-0.3:1, and can further be 0.01-0.02:1.

[0036] The temperature of the phosphating reaction is 300-500°C; further, it can be 300-400°C.

[0037] The phosphating reaction time can be adjusted as needed, for example, it can be 0.5 to 5 hours, and further can be 0.5 hours, 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours or 5 hours.

[0038] In the present invention, the cationic membrane is a conventional membrane with cation selectivity, such as Nafion 117 or Fumasep FS-9100-PK.

[0039] In the present invention, in the electrolyte B, the water-soluble sulfide B is at least one of sodium sulfide, potassium sulfide, ammonium sulfide, sodium hydrogen sulfide, and potassium hydrogen sulfide;

[0040] Base B includes at least one of sodium hydroxide and potassium hydroxide;

[0041] There is no particular requirement for the concentration of the components in the electrolyte B. For example, the concentration of the water-soluble sulfide B is 1-4 M, and may further be 1.5-2.5 M, and the concentration of the base B is 1-1.5 M.

[0042] In the present invention, the electrolyte B may be industrial wastewater containing the water-soluble sulfide B and alkali B.

[0043] In the present invention, the cell voltage during the electrolysis process is 0.5-2 V; further, it can be 0.9-1.8 V. The current density is 10-1000 mA / cm 2 , further can be 100~400 mA / cm 2 ; further can be 250~350 mA / cm 2 .

[0044] In the present invention, the optional leaching process reaction is, for example:

[0045] ;

[0046] ;

[0047] In the present invention, the reaction of the optional electrolysis process is:

[0048] Cathode reaction: ;

[0049] Anodic reaction: ( ).

[0050] Beneficial effects

[0051] (1) The present invention provides a coupled electrolysis method of sulfur oxidation-antimony reduction, which can effectively improve the efficiency and purity of antimony preparation, improve the electricity utilization rate, and significantly reduce costs.

[0052] (2) The present invention is based on the combination of sulfur oxidation and antimony reduction coupled electrolysis, and further cooperates with the joint control of anode materials, which is expected to further improve the coupling effect of sulfur oxidation and antimony reduction, further improve the efficiency, purity and yield of antimony preparation, and reduce energy consumption. BRIEF DESCRIPTION OF THE DRAWINGS

[0053] Figure 1 1 is the XRD pattern of the anodes obtained in Examples 1, 5, 6 and 7.

[0054] Figure 2 This is the SEM image of the anode obtained in Example 1.

[0055] Figure 3 This is a TEM image of the anode obtained in Example 1. DETAILED DESCRIPTION

[0056] The following embodiments do not limit the scope of the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

[0057] The antimony concentrate used is taken from stibnite in a certain place, and the antimony grade is about 26±1%.

[0058] The electrolytic cell of the present invention comprises a container, wherein the container is divided into an anode chamber and a cathode chamber by a cationic diaphragm, the anode chamber is provided with an anode, and the cathode chamber is provided with a cathode, wherein the anode is compounded with a sulfur ion oxidation catalyst.

[0059] During the electrolysis process, electrolyte A is added to the cathode chamber and electrolyte B is added to the anode chamber, and then the anode and cathode are conductively connected (the anode is conductively connected to the positive pole of the power supply, and the cathode is conductively connected to the negative pole of the power supply). Among them, electrolyte A is antimony leaching solution, and electrolyte B is an aqueous solution dissolved with sulfide and alkali.

[0060] The following are typical cases:

[0061] Example 1

[0062] Step 1:

[0063] 100 g of antimony concentrate powder was mixed with a leachate for leaching. The leaching temperature was 60°C, the leachate contained 50 g / L of Na2S, 25 g / L of NaOH (alkali), and a liquid-to-solid ratio of 4:1 (mL / g). After 30 minutes of leaching, the mixture was filtered to obtain a filtrate. The filter cake was then washed with water (the liquid-to-solid ratio during the washing stage was 1-2 mL / g) to obtain a washing solution. The washing solution and filtrate were combined to obtain a leachate (controllable to 62.5 g / L of Sb, 50 g / L of sodium sulfide, and 25 g / L of sodium hydroxide). The filter residue was dried and weighed. The antimony content in the leachate and filter residue was analyzed.

[0064] Step 2:

[0065] anode:

[0066] Step a: Immerse an iron foam substrate (length, width, and height of 30 mm, 15 mm, and 2 mm, respectively) in a 0.1 mol / L Co(NO3)2 solution (the weight ratio of iron in the iron substrate to cobalt in cobalt nitrate is 1:0.01) at 90°C for 24 h.

[0067] Step b: Subsequently, the foamed iron substrate after the reaction in step a was immersed in a mixed solution of 1 M NaBH4 and 1 M NaOH (the molar ratio of Co, NaBH4, and NaOH was 1:10:10) and reacted (liquid phase reaction) at room temperature (26°C) for 6 h to obtain a precursor electrode;

[0068] Step c: Finally, the precursor electrode after the reaction in step b was mixed with sodium hypophosphite (P / Co molar ratio of 0.017:1) in an argon atmosphere and heat treated at 320±5°C for 2 h to deposit B and P co-modified cobalt ferrite on the foam iron to obtain an anode (labeled as BP-CFO); then the anode was cut to the required size.

[0069] Cathode: steel plate;

[0070] The distance between the anode and cathode is 1 cm;

[0071] Electrolyte A: leachate from step 1;

[0072] Electrolyte B: an aqueous solution containing 2 M Na2S and 1 M NaOH;

[0073] Cationic membrane: Nafion 117;

[0074] During the electrolysis process, the temperature was 30 °C and the current density was 300 mA / cm 2 , electrode area 1 cm 2 , electrodeposition for 70 h.

[0075] Example 2

[0076] Compared with Example 1, the only difference is that the alkali used in the leaching process is changed to KOH, and its molar amount is the same as Example 1. Other operations and parameters are the same as Example 1.

[0077] Example 3

[0078] Compared with Example 1, the only difference is that the leaching conditions are changed as follows: the concentration of Na2S is 60 g / L, the concentration of NaOH is 30 g / L, the liquid-solid ratio is 5:1 (mL / g), the leaching temperature is 70°C, the leaching time is 40 min, and the concentration of Sb in the leachate is controlled to be 63.1 g / L, the concentration of sodium sulfide is 60 g / L, and the concentration of sodium hydroxide is 30 g / L; other operations and parameters are the same as in Example 1.

[0079] Example 4

[0080] Compared with Example 1, the only difference is that the electrodeposition conditions are changed to: interelectrode distance 1 cm, temperature 25 °C, current density 200 mA / cm 2 , electrode area 1cm 2 , electrodeposition for 50 h.

[0081] Example 5

[0082] Compared with Example 1, the only difference is that the anode is a cobalt ferrite self-supporting anode, and the cobalt ferrite is not B / P modified. That is, during the anode preparation process, the only difference is that NaBH4 is not added in the liquid phase reaction in step b, and sodium hypophosphite is not added during the subsequent heat treatment in step c. The other operations and parameters are the same as in Example 1. The cobalt ferrite catalyst is obtained on the foam iron substrate, and the obtained anode is marked as CFO. The other operations and parameters are the same as in Example 1.

[0083] Example 6

[0084] Compared with Example 1, the only difference is that the anode is a boron-modified cobalt ferrite self-supporting anode, and the cobalt ferrite is not P-modified. That is, during the anode preparation process, the only difference is that sodium hypophosphite is not added during the subsequent step c heat treatment, and a B-modified cobalt ferrite catalyst is obtained on the foam iron substrate. The obtained anode is marked as B-CFO, and the other operations and parameters are the same as in Example 1.

[0085] Example 7

[0086] Compared with Example 1, the only difference is that the anode is a phosphorus-modified cobalt ferrite self-supporting anode, and the cobalt ferrite is not B-modified. That is, during the anode preparation process, the only difference is that NaBH4 is not added during the liquid phase reaction in step b, and a P-modified cobalt ferrite catalyst is obtained on the foam iron substrate. The obtained anode is marked as P-CFO, and the other operations and parameters are the same as in Example 1.

[0087] Example 8

[0088] Compared with Example 1, the only difference is that B / P is modified through a heat treatment, and the different anode catalyst preparation conditions are: the foam iron substrate is immersed in a 0.1 mol / L Co(NO3)2 solution and kept warm at 90°C for 24 hours; then, the foam iron substrate after the reaction is completed, boric acid and sodium hypophosphite (the amounts of boron and phosphorus are the same as in Example 1) are mixed, and heat-treated (temperature is the same as in Example 1) for 2 hours to obtain a B and P co-doped cobalt ferrite catalyst, which is directly used as the anode. The other operations and parameters are the same as in Example 1.

[0089] Example 9

[0090] Compared with Example 1, the only difference is that the cationic membrane model used in the electrolysis process is changed to Fumasep FS-9100-PK.

[0091] Example 10

[0092] Compared to Example 1, the only difference lies in the changes in the anode catalyst preparation conditions. Specifically, in step a, the weight ratio of iron in the iron substrate to cobalt in the cobalt nitrate was 1:0.02, the reaction temperature was 60°C, and the reaction time was 48 hours. In step b, the molar ratio of Co, NaBH4, and NaOH was 1:8:8, and the liquid-phase reaction time was 8 hours. In step c, the P / Co molar ratio was 0.02:1, and the heat treatment was carried out at 340±5°C for 2.5 hours. All other operations and parameters were the same as in Example 1.

[0093] Comparative Example 1

[0094] Compared with Example 1, the only difference is that the type of ion exchange membrane used in the electrolysis process is changed:

[0095] Group A: No diaphragm is used in the electrolytic cell;

[0096] Group B: ordinary porous diaphragm (asbestos diaphragm) is used in the electrolytic cell;

[0097] Group C: Anion exchange membrane (FAA-3-50) was used for separation in the electrolytic cell.

[0098] Other operations and parameters are the same as in Example 1.

[0099] Comparative Example 2

[0100] Compared with Example 1, the only difference is that, during the electrolysis process, the anode is the foamed iron in step a, and the other operations and parameters are the same as those in Example 1.

[0101] Comparative Example 3

[0102] Compared with Example 1, the only difference is that the anode electrolyte does not contain sodium sulfide during the electrodeposition process.

[0103] The effects of each case are shown in Table 1;

[0104]

[0105] As shown in Table 1, the combined electrolysis of sulfur oxidation and antimony reduction, combined with the coordinated control of anode materials, is expected to further improve the coupling effect of sulfur oxidation and antimony reduction, further improve the efficiency, purity, and yield of antimony preparation, and reduce energy consumption. Furthermore, Examples 1, 5, and 8 show that the anodes obtained using the B-first, P-later modification scheme described in the present invention further optimize the synergistic coupling of sulfur oxidation and antimony deposition, further enhancing the effects and further reducing energy consumption.

[0106] Comparative Examples 1 to 3 did not adopt the electrolysis process of the present invention, and did not achieve the coupling of sulfide ion and antimony reduction. The antimony precipitation amount and quality were low, and the Faraday efficiency under the same amount of electricity was far lower than that of the solution of the present invention. This also shows that the method of the present invention can obtain better Faraday efficiency, better antimony electrolysis efficiency and effect, and in addition, it has lower alkali consumption and has excellent industrial application prospects.

Claims

1. A method for antimony hydrometallurgy coupled with sulfide ion oxidation reaction, comprising leaching antimony concentrate in a leaching agent comprising a water-soluble sulfide A and an alkali A to produce an antimony-containing leachate; and electrolyzing the antimony-containing leachate in an electrolytic cell; characterized in that: The electrolytic cell comprises a container and a cationic diaphragm that separates the container into an anode chamber and a cathode chamber; the cathode chamber is provided with a cathode, and the anode chamber is provided with an anode compounded with a sulfur ion oxidation catalyst; During the electrolysis process, an antimony-containing leachate is placed in the cathode chamber as electrolyte A, and a solution containing a water-soluble sulfide B and an alkali B is placed in the anode chamber as electrolyte B. The anode and cathode are then conductively connected to perform electrolysis, so that antimony is deposited in the cathode chamber to form antimony. During this process, sulfur ions are oxidized in the anode chamber. The sulfur ion oxidation catalyst in the anode includes cobalt ferrite and / or modified cobalt ferrite; the modified cobalt ferrite is cobalt ferrite modified with boron and / or phosphorus.

2. The antimony hydrometallurgical method coupled with sulfide ion oxidation reaction according to claim 1, characterized in that: In the leaching agent, the water-soluble sulfide A is at least one of sodium sulfide and potassium sulfide; Base A includes at least one of sodium hydroxide and potassium hydroxide; In the leaching agent, the concentration of water-soluble sulfide A is 20~80 g / L, and the concentration of alkali A is 10~160 g / L.

3. The antimony hydrometallurgical method coupled with sulfide ion oxidation reaction according to claim 1 or 2, characterized in that: The temperature of the leaching process is 30~150℃; the liquid-to-solid ratio in the leaching stage is 1~10mL / g; The leaching time is 0.5~5h.

4. The antimony hydrometallurgical method coupled with sulfide ion oxidation reaction according to claim 1, characterized in that: The cathode is graphite, a conductive metal plate or a conductive alloy plate.

5. The antimony hydrometallurgical method coupled with sulfide ion oxidation reaction according to claim 1, characterized in that: The anode is a self-supporting electrode compounded with a sulfur ion oxidation catalyst, and its preparation steps are as follows: The iron substrate and the cobalt source are subjected to a first-stage reaction, followed by a second-stage reaction with borohydride and alkali, and then a phosphating reaction is performed to obtain the product.

6. The antimony hydrometallurgy method coupled with sulfide ion oxidation reaction according to claim 5, characterized in that: The iron substrate is an iron sheet, foamed iron, an iron alloy sheet or foamed iron alloy; The cobalt source is a water-soluble cobalt salt; The borohydride is at least one of sodium borohydride, potassium borohydride, and ammonium borohydride; The base is an alkali metal hydroxide; The phosphorus source for the phosphating reaction includes solid, liquid or gaseous phosphorus-containing raw materials.

7. The antimony hydrometallurgical method coupled with sulfide ion oxidation reaction according to claim 6, characterized in that: The weight ratio of the cobalt element in the iron substrate and the cobalt source is 1:0.005~0.1; The molar ratio of cobalt source, borohydride and base is 1:5~20:5~20; The molar ratio of P in the phosphorus source to cobalt in the cobalt source is 0.01-0.3:1; The temperature of the phosphating reaction is 300-500°C.

8. The antimony hydrometallurgy method coupled with sulfide ion oxidation reaction according to claim 1, characterized in that: The cationic membrane is a membrane with cation selectivity; In the electrolyte B, the water-soluble sulfide B is at least one of sodium sulfide, potassium sulfide, ammonium sulfide, sodium hydrogen sulfide, and potassium hydrogen sulfide; Base B includes at least one of sodium hydroxide and potassium hydroxide; In the electrolyte B, the concentration of the water-soluble sulfide B is 1 to 4 M, and the concentration of the base B is 0.5 to 2 M.

9. The antimony hydrometallurgy method coupled with sulfide ion oxidation reaction according to claim 1, characterized in that: The cell voltage during electrolysis is 0.5~2 V; the current density is 10~1000 mA / cm 2 .

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