An electrochemical metallurgical method for extracting metal and sulfur from metal sulfides

Abstract

The present invention relates to an electrochemical metallurgical method for extracting metal and sulfur from metal sulfide, and belongs to the technical field of metallurgy and chemical industry. The present invention prepares metal sulfide into an electrode, namely a metal sulfide electrode, and adjusts the composition and mechanical properties of the metal sulfide during the preparation process; the metal sulfide electrode is used as the anode, and the anode and the cathode are inserted into the electrolyte at intervals to form an electrode array for electrolysis, and the sulfur element in the metal sulfide is oxidized and adsorbed on the anode in the form of sulfur element, and the metal ions enter the electrolyte and undergo a reduction reaction on the cathode surface to generate metal element, wherein the cathode is titanium, copper, stainless steel, lead, zinc, aluminum or graphite. The present invention puts the metal sulfide electrode into the electrolyte for electrolysis to obtain cathode metal and anode sulfur, and realizes the extraction of metal and sulfur, which has the characteristics of small environmental pollution, low investment and simple process.

Description

Technical Field

[0001] The invention relates to an electrochemical metallurgical method for extracting metal and sulfur from metal sulfide, belonging to the technical field of metallurgy and chemical industry. Background Art

[0002] Sulfides are the main source of extracting most metals and have important economic value. More than 300 kinds of sulfides have been discovered in nature. In modern metallurgy, the treatment methods of metal sulfides are mostly high-temperature chemical processes. However, the method of extracting metals from metal sulfides is more complicated than that of oxide ores, mainly because sulfides cannot be directly reduced to metals with carbon. There are three main ways to extract metals from metal sulfides: one is through oxidative roasting, and then through reduction or other methods to obtain metals or alloys; the second is through matte smelting, and then through blowing, refining and other methods to obtain metals; the third is through sulfuric acid roasting, and then through leaching, electrolysis and other methods to obtain metals.

[0003] Oxidative roasting of metal sulfides is to heat metal sulfides below their melting point to oxidize them and turn them into metal oxides. The purpose is to remove part or all of the sulfur in the metal sulfides. The sulfur escapes as sulfur dioxide smoke. The obtained metal oxides are reduced to metals or alloys using a reducing agent, or the metals are extracted by leaching, electrolysis, and other methods. For example, lead metallurgy is to convert lead sulfide and other sulfides in lead sulfide concentrate into lead-containing oxides under high temperature and oxidizing atmosphere, and then use carbon to reduce them to crude lead, which is then refined and purified; for another example, zinc metallurgy is to remove as much sulfur as possible from zinc sulfide concentrate through oxidative roasting, convert zinc sulfide into zinc oxide, and then extract zinc through electrolysis after leaching with sulfuric acid. Oxidative roasting is also widely used in the extraction of metals such as antimony and mercury.

[0004] Metal sulfides, such as copper sulfide ore, are often associated with iron sulfides. Such metal sulfides are mostly extracted by matte smelting process. The principle of matte smelting is to use the characteristics that the main metal has a higher affinity for sulfur than iron or some impurity metals, while the affinity of iron for oxygen is greater than that of the main metal. Under high temperature and controlled oxidizing atmosphere conditions, iron is oxidized to ferrous oxide, and then slag is removed with gangue, flux, etc., so that the metal and sulfur or several metal sulfides are mutually fused into matte. Since the oxidizing atmosphere is controlled during matte smelting, only a small amount of sulfur is converted into sulfur dioxide, and most of the sulfur is retained in the matte. For example, copper matte is produced by this process. The matte is then used to extract metals through processes such as blowing and refining. During the blowing process, sulfur is converted into sulfur dioxide. Matte smelting is also used in the extraction of metals such as lead, molybdenum, antimony, bismuth, and cobalt.

[0005] The sulphate roasting of metal sulfides mainly utilizes the differences in decomposition temperature, compound boiling point and water solubility between sulfates. By controlling the appropriate temperature, the metal compounds are converted into sulfates or enter the gas phase, and some sulfates are decomposed into water-insoluble oxides. Then the metals are extracted by directional separation of metals by leaching or recovery of smoke. For example, the pyrometallurgy of copper-cobalt concentrate is to convert valuable metals such as copper and cobalt in the charge into water-soluble sulfates, convert sulfur into sulfur dioxide, and convert iron into ferric oxide as much as possible under strict control of the furnace atmosphere and furnace temperature. Copper sulfate, cobalt sulfate, etc. are then used to obtain metals or alloys through electrolysis and other methods. Sulphate roasting is also used in the extraction of metals such as zinc, nickel, and vanadium.

[0006] In summary, in the treatment of metal sulfides, sulfur is mostly oxidized to sulfur dioxide. Sulfur dioxide can cause serious pollution to the atmosphere, so metallurgical enterprises must build flue gas desulfurization facilities; most of the recovered sulfur dioxide is used to prepare sulfuric acid, but sulfuric acid has complicated transportation procedures and limited transportation distances, and is not suitable for long-term storage. Furthermore, lead, antimony, etc. will also produce carbon dioxide during smelting, which is not conducive to achieving the goals of carbon emission reduction and carbon peak. Summary of the invention

[0007] The present invention aims at the problem of processing metal sulfides and proposes an electrochemical metallurgical method for extracting metal and sulfur from metal sulfides. The present invention places a metal sulfide electrode into an electrolyte for electrolysis to obtain cathode metal and anode sulfur, thereby realizing the extraction of metal and sulfur, reducing harmful gases such as sulfur dioxide generated during the smelting process, alleviating environmental pressure, and reducing the import volume of sulfur. The method has the characteristics of short process, low investment, and no sulfur dioxide pollution.

[0008] An electrochemical metallurgical method for extracting metal and sulfur from metal sulfides, the specific steps are as follows:

[0009] (1) Preparing metal sulfide into an electrode, i.e., a metal sulfide electrode, during the preparation process, the metal sulfide composition can be adjusted by adding elements, and the mechanical properties can be adjusted by adding reinforcing agents; wherein the added elements are one or more of copper, manganese, cobalt, sulfur, molybdenum, tin, bismuth, lead, zinc, selenium, antimony, tellurium, and cadmium, and the mass of the added elements is 0 to 50% of the mass of the metal sulfide; the reinforcing agent is carbon fiber, stainless steel fiber, copper fiber, or lead fiber, and the mass of the reinforcing agent is 0 to 10% of the mass of the metal sulfide;

[0010] Preferably, the added element is one or more of copper, sulfur, and tin, and the mass of the added element is 5% to 15% of the mass of the metal sulfide;

[0011] Preferably, the reinforcing agent is carbon fiber or stainless steel fiber, and the mass of the reinforcing agent is 0.5% to 1% of the mass of the metal sulfide;

[0012] Most metal sulfides are semiconductors. When metal sulfides of n-type semiconductors are used as anodes, they are limited by themselves and have poor conductivity at the anode. To ensure smooth electrolysis at the anode, their composition is adjusted to transform them into p-type semiconductors. When natural sulfide concentrates, metallurgical intermediates or by-products are used as anodes, they have poor conductivity due to high impurity content. To ensure smooth electrolysis at the anode, the content of the elements they contain is adjusted to increase their conductivity. Metal sulfides are generally brittle, and the prepared electrodes are prone to breakage during the electrolysis process. The mechanical strength of the metal sulfides can be increased by changing the ratio of the elements they contain or adding materials such as carbon fiber during the preparation process.

[0013] (2) A metal sulfide electrode is used as the anode, and the anode and cathode are inserted into the electrolyte at intervals to form an electrode array. The distance between the electrodes, the cell voltage, the current density, the electrolyte temperature and the circulation speed are adjusted to perform electrolysis. The sulfur element in the metal sulfide is oxidized and adsorbed on the anode in the form of sulfur element. The metal ions enter the electrolyte and undergo a reduction reaction on the cathode surface to generate metal element, and the products of the anode and cathode are stripped. The cathode is made of titanium, copper, stainless steel, lead, zinc, aluminum or graphite, and the longitudinal cross-sectional shape of the cathode corresponds to that of the anode. The longitudinal cross-sectional shape is square, circular, triangular, trapezoidal, pentagonal or fan-shaped, and the longitudinal cross-sectional area is 1 cm 2 ~10m 2 ; The thickness or radius of the cathode is 0.2 to 3000 mm;

[0014] Preferably, the cathode is made of titanium, copper, stainless steel, lead or aluminum, and has a square longitudinal section with a longitudinal section area of ​​200 cm 2 ~0.6m 2 , the thickness of the cathode is 1.5 to 6 mm;

[0015] The number n of the anodes is in the range of 1 to 1000, and the number of the cathodes is n+1; preferably, the number n of the anodes is in the range of 35 to 350;

[0016] The metal sulfide is a pure substance or a mixture. The pure substance includes but is not limited to lithium sulfide, sodium sulfide, magnesium sulfide, aluminum sulfide, potassium sulfide, calcium sulfide, manganese sulfide, iron sulfide, ferrous sulfide, cobalt sulfide, copper sulfide, cuprous sulfide, zinc sulfide, molybdenum sulfide, silver sulfide, cadmium sulfide, stannous sulfide, antimony sulfide, lead sulfide, and bismuth sulfide; the mixture is a natural sulfide concentrate, a metallurgical intermediate or by-product. The natural sulfide concentrate includes but is not limited to pyrite, chlorovanadate, chalcopyrite, bornite, chalcocite, covellite, chalcopyrite, tetrahedrite, tetrahedrite, sulfur Arsenic copper ore, sulfide copper cobalt ore, sulfide cobalt ore, arsenic cobalt ore, tungsten ore, sulfide tin ore, stannite, cylindrical tin ore, sulfide tin lead ore, stibnite tin lead ore, disulfide tin ore, rhombic sulfide tin ore, sulfide manganese ore, molybdenite, iron molybdenite, sulfide molybdenite, sphalerite, wurtzite, galena, sulfide antimonite, wheel ore, bismuthinite, sulfide bismuth tellurite, brittle sulfide bismuth ore, sulfide bismuth selenite, sulfide copper bismuth ore, chalcocite bismuth ore, stibnite, brittle sulfide lead antimonite, antimony tetrahedrite; metallurgical intermediates or by-products include but are not limited to copper matte, cobalt matte, lead copper matte, antimony matte, iron matte, copper molybdenum matte, bismuth matte.

[0017] Preferred metal sulfides include sodium sulfide, tin sulfide, aluminum sulfide, antimony sulfide, bismuthinite, manganese sulfide, sphalerite, galena, and copper matte.

[0018] The preparation method of the metal sulfide electrode is thermal spraying, hot plating, physical vapor deposition, chemical vapor deposition, casting or powder metallurgy. The physical vapor deposition method includes but is not limited to vacuum evaporation and magnetron sputtering; the casting method includes but is not limited to sand casting and full mold casting; the powder metallurgy method includes but is not limited to press method and centrifugal forming method.

[0019] Preferably, thermal spraying method: using a heat source to melt the metal sulfide powder, spraying it onto the surface of the substrate by controlling the pressure of the protective gas to form a metal sulfide electrode, wherein the pressure is 1 to 20 MPa; the heat source is preferably plasma arc heating, and the pressure is preferably 5 to 15 MPa;

[0020] Vacuum evaporation method: Add metal sulfide powder into the evaporation container, adjust the vacuum degree, and heat to deposit the powder on the substrate to obtain the metal sulfide electrode. The vacuum degree is 10 -6 ~10 2 Pa; the heating method is preferably resistance heating;

[0021] Magnetron sputtering method: connect the substrate to the anode, connect the metal sulfide target to the cathode, and evacuate to 10 -3 Pa, fill with argon to maintain the vacuum degree at 10 -2In the range of 10 Pa to 10 Pa, power is supplied, and metal sulfide electrodes are obtained by magnetron sputtering, wherein the material of the sulfide target includes but is not limited to magnesium sulfide, zinc sulfide, calcium sulfide, aluminum sulfide, and cadmium sulfide; the sulfide target is preferably aluminum sulfide;

[0022] Chemical vapor deposition method: a protective gas is filled into a chemical vapor deposition device, metal powder and sulfur powder are placed in an evaporator, the metal powder and sulfur powder are heated to evaporate and enter the reaction chamber to react, and then deposited on a substrate to obtain a metal sulfide electrode; the protective gas is preferably argon;

[0023] Hot-dip method: Use a smelting furnace to melt the metal sulfide, insert the substrate into the liquid metal sulfide for hot-dip to obtain a metal sulfide electrode;

[0024] Sand casting method: Use molding sand and core sand to prepare a mold cavity, melt the metal sulfide in a smelting furnace, pour it into the mold cavity, cool and solidify, and obtain the metal sulfide electrode by sand dropping and cleaning;

[0025] Full-mold casting method: bury the foam plastic in sand, melt the metal sulfide in a smelting furnace, replace the foam plastic with the metal sulfide melt, cool and solidify, and obtain the metal sulfide electrode by sand dropping and cleaning;

[0026] When the hot-dip method, sand casting method or full mold casting method is adopted, the melting furnace is preferably a vacuum induction furnace, a vacuum arc furnace, an induction furnace or a reverberatory furnace;

[0027] Press method: the metal sulfide powder and the forming agent are mixed evenly and then loaded into a mold, and pressed to obtain a green body, and the green body is sintered to obtain a metal sulfide electrode, wherein the pressing pressure is 10-30MPa, the pressing speed is 1-15mm / s, and the holding time is 0.1-10h; the pressure is preferably 20-25MPa, the pressing speed is preferably 10-12mm / s, and the holding time is preferably 1.5-2h;

[0028] Centrifugal forming method: the metal sulfide powder and the forming agent are mixed evenly and then loaded into a mold, and the green body is obtained by centrifugal forming, and the green body is sintered to obtain a metal sulfide electrode, wherein the speed of the centrifugal forming is 500-4500r / min; the speed is preferably 3000-3500r / min;

[0029] The sintering atmosphere is a protective gas atmosphere, the sintering temperature is 400-1200° C., and the sintering time is 0.1-10 hours; preferably, the sintering temperature is 750-1200° C., and the sintering time is 1.5-2 hours.

[0030] Protective gases include but are not limited to argon, nitrogen, and carbon dioxide;

[0031] The average particle size of the metal sulfide powder is 1 nm to 1 mm.

[0032] The material of the substrate is metal, graphite or composite material. The material of the metal substrate includes but is not limited to copper, zinc, lead, tin, aluminum, titanium, stainless steel, aluminum alloy, lead alloy, titanium alloy, manganese alloy, copper alloy, zinc alloy, tin alloy, tungsten alloy, molybdenum alloy. The material of the composite substrate includes but is not limited to conductive silicone rubber, conductive plastic, conductive fiber; the substrate is preferably titanium, stainless steel, titanium alloy, lead alloy or conductive fiber;

[0033] The substrate has two ears, and the longitudinal section shape other than the two ears is square, circular, triangular, trapezoidal, pentagonal, fan-shaped, fence-shaped or porous, and the longitudinal section area of ​​the substrate is 1cm 2 ~10m 2 , thickness or radius is 1 to 2000 mm, and the thickness of the metal sulfide attached to the substrate is 1 to 30 mm;

[0034] The longitudinal cross-sectional shape of the substrate is preferably square, circular, triangular, fence-shaped or porous, and the longitudinal cross-sectional area is preferably 180 cm 2 ~0.35m 2 , the thickness or radius is preferably 1 to 3 mm; the thickness of the metal sulfide on the substrate is preferably 3 to 20 mm;

[0035] The metal sulfide electrode prepared by casting and powder metallurgy is in the shape of a cuboid with two ears, with a length ranging from 100 to 2500 mm, a width ranging from 100 to 2000 mm, and a thickness ranging from 1 to 100 mm; preferably, the length is 800 to 1200 mm, the width is 500 to 700 mm, and the thickness is 45 to 60 mm.

[0036] The forming agent includes but is not limited to starch, sulfur, molybdenum disulfide, graphite powder, paraffin, and rosin; the forming agent is preferably sulfur or graphite powder.

[0037] The electrolyte contains a solvent, an electrolyte, an oxidant, and an additive. The solvent is water or an organic solvent. The organic solvent is one or more of anhydrous acetic acid, methanol, acetonitrile, and tetrahydrofuran. Preferably, the organic solvent is one or more of methanol, acetonitrile, and tetrahydrofuran.

[0038] The electrolyte is one or more of sulfuric acid, perchloric acid, hydrobromic acid, hydrochloric acid, silicic acid, carbonic acid, phosphoric acid, nitrous acid, hydroiodic acid, tartaric acid, oxalic acid, citric acid, hydrofluoric acid, acetic acid, hypochlorous acid, boric acid, bismuth chloride, bismuth sulfate, bismuth fluorosilicate, sodium chloride, lithium perchlorate, magnesium perchlorate, molybdenum chloride, sodium sulfate, aluminum chloride, sodium nitrate, molybdenum sulfate, copper chloride, copper sulfate, lead chloride, lead fluorosilicate, cadmium chloride, antimony chloride, silver nitrate, stannous sulfate, zinc chloride, sodium acetate, sodium nitrite, sodium borate, zinc sulfate, manganese chloride, cobalt chloride, ammonium sulfate, cobalt sulfate, sodium oxalate, sodium tetrafluoroborate, sodium sulfide, sodium hydroxide, calcium sulfonate, potassium methoxide, aluminum stearate, ammonium chloride, and tetraethylammonium tetrafluoroborate; the electrolyte content in the electrolyte is 0.1-1000g / L;

[0039] Preferably, the electrolyte is one or more of sulfuric acid, hydrochloric acid, silicic acid fluoride, sodium tetrafluoroborate, sodium chloride, stannous sulfate, aluminum chloride, ammonium chloride, sodium sulfide, sodium hydroxide, bismuth chloride, bismuth silicofluoride, manganese chloride, ammonium sulfate, zinc sulfate, zinc chloride, lead chloride, lead fluorosilicate, copper sulfate, and copper chloride, and the electrolyte content in the electrolyte is 10 to 240 g / L;

[0040] The oxidant is one or more of ferric chloride, potassium permanganate, oxygen, hydrogen peroxide, fluorine, ozone, ferric sulfate, chlorine, bromine vapor, sodium dichromate. When the oxidant is a gas, the flow rate is 0.01 to 5 L / min. When the oxidant is a non-gas, the oxidant content in the electrolyte is 0.1 to 1000 g / L.

[0041] Preferably, the oxidant is one or more of sodium perchlorate, ferric chloride, potassium permanganate, oxygen, hydrogen peroxide, ferric sulfate, and sodium hypochlorite; when the oxidant is oxygen, the flow rate is 0.1 to 0.15 L / min, and when the oxidant is non-gas, the oxidant content in the electrolyte is 10 to 45 g / L;

[0042] The additive is one or more of gelatin, bone glue, hide glue, thiourea, β-phenol, powder glue, sodium lignosulfonate, carbolic acid, tannin, diphenylamine, phenol, borax, and casein, and the content of the additive in the electrolyte is 0 to 1000 g / L; when the content of the additive is 0, the electrolyte does not contain the additive;

[0043] Preferably, the additive is one or more of gelatin, bone glue, thiourea, β-phenol, cresol sulfonic acid, sodium lignosulfonate, and casein.

[0044] When the electrolyte contains additives, the preferred content of the additives is 8 to 30 mg / L;

[0045] The distance between the same plates is 1 to 1000 mm, the cell voltage range is 0.1 to 10 V, and the current density control range is 1 to 1000 A / m 2, the electrolyte temperature range is 25~100℃, the circulation speed range is 1~100L / min, and the anode residual rate is 1%~25%;

[0046] Preferably, the distance between the same plates is 18-120 mm, the cell voltage range is 1.5-3.5 V, and the current density control range is 150-450 A / m 2 , the electrolyte temperature range is 25-60℃, the circulation speed range is 5-30L / min, and the anode residual rate is 5%-20%;

[0047] The method for peeling the product is ultrasonic method, mechanical method or manual method.

[0048] The principle of extracting metals and sulfur from metal sulfides: From a physical point of view, according to the principle of semiconductor electrochemistry, when the semiconductor is n-type, the carriers are free electrons. When the cathode is polarized, there are more free electrons in the conduction band than when no potential is applied, and the reaction can proceed smoothly in the conduction band. However, for the anode polarization of the n-type semiconductor, the minority holes in the valence band flow from the body to the semiconductor / electrolyte interface to participate in the reaction, while the majority electrons in the conduction band are repelled and flow to the inside of the semiconductor and away from the interface. As the polarization increases, the rate at which electrons in the conduction band participate in the cathode reaction (i c ) increases, and finally the electron concentration at the semiconductor / electrolyte interface is even less than the hole concentration. At this time, if an oxidation reaction is required on the n-type semiconductor electrode, it depends on the generation and diffusion of holes inside the semiconductor. However, the generation and diffusion rate of carriers is constant, so at this time, the rate that determines the electrode reaction is c The value is no longer the carrier movement rate but the internal carrier diffusion rate and generation rate, showing the current "self-limiting effect", that is, i c The value reaches the so-called saturation current value i s . Therefore, in the electrolysis process, when the anode is a semiconductor, the semiconductor type should not be n-type. Similarly, when cathode polarization is performed in the valence band of a p-type semiconductor, the current will also be limited, and saturation current can also be observed. However, when an oxidation reaction occurs at a p-type semiconductor electrode, there is no current "self-limiting effect", and the anodic polarization reaction can proceed smoothly in the valence band. Therefore, in the electrolysis process, p-type semiconductors are more suitable as anodes; the typical polarization curves of n-type semiconductors and p-type semiconductors can be seen in Figure 1 ;(i v represents the rate at which holes in the valence band participate in the electrode reaction)

[0049] From a chemical perspective, when the oxidizing agent (such as hydrogen peroxide) is more oxidizing than the metal sulfide (Me2S x ) 2- When the oxidant can 2-Oxidized to sulfur, the relevant reaction equation is shown in (1); at the same time, when the metal sulfide is the anode, a positive voltage is applied, and an oxidation reaction occurs at the anode, the relevant reaction equation is shown in (2); the sulfur element in the metal sulfide is oxidized and adsorbed on the anode plate in the form of sulfur. As the sulfur element is oxidized, the metal ions enter the electrolyte and undergo a reduction reaction on the cathode surface to generate metal, the relevant reaction equation is shown in (3).

[0050] Me2S x +xH2O2+2xH + →2Me x+ +xS+2xH2O (1)

[0051] Me2S x -2xe - →2Me x+ +xS (2)

[0052] Me x+ +xe - →Me (3)

[0053] The beneficial effects of the present invention are:

[0054] (1) The present invention places a metal sulfide electrode into an electrolyte for electrolysis to obtain cathode metal and anode sulfur, thereby extracting metal and sulfur, reducing harmful gases such as sulfur dioxide generated during the smelting process, alleviating environmental pressure, and reducing the import volume of sulfur. The process is short, the investment is low, and no sulfur dioxide pollution is generated;

[0055] (2) The present invention adjusts the semiconductor type of the metal sulfide electrode to p-type, so that the metal sulfide electrode will not have a current "self-limiting effect" during anode electrolysis;

[0056] (3) The present invention increases the conductivity of the electrode by adding adjustment elements during the preparation of the metal sulfide electrode, which is beneficial for the metal sulfide electrode to use a smaller cell voltage during anode electrolysis and obtain a larger current density;

[0057] (4) The present invention adds a reinforcing agent during the preparation process of the metal sulfide electrode to increase the mechanical properties of the electrode, which is beneficial to reducing the residual electrode rate of the metal sulfide electrode and alleviating the production labor intensity. BRIEF DESCRIPTION OF THE DRAWINGS

[0058] Figure 1 are typical polarization curves for n-type semiconductors and p-type semiconductors;

[0059] Figure 2 The cyclic voltammetry curve of the metal sulfide in the electrolyte of Example 13;

[0060] Figure 3This is a morphology of the cathode product copper of Example 13 under a scanning electron microscope;

[0061] Figure 4 This is the Raman diagram of the anode product sulfur of Example 13;

[0062] Figure 5 This is the XRD diagram of the anode product sulfur in Example 13. DETAILED DESCRIPTION

[0063] The present invention is further described in detail below in conjunction with specific implementation modes, but the protection scope of the present invention is not limited to the described contents.

[0064] Example 1: An electrochemical metallurgical method for extracting metal and sulfur from metal sulfides, the specific steps are as follows:

[0065] (1) A sodium sulfide anode was prepared by thermal spraying, wherein the sodium sulfide (Na2S) was a product of a chemical plant in Shanghai, and its sodium sulfide content was ≥60%; the sodium sulfide particle size was 80 μm, the heat source was plasma arc heating, and the nitrogen pressure was 10 MPa; the substrate material was titanium, the longitudinal cross-section was triangular, and the longitudinal cross-sectional area was 500 cm 2 , thickness is 1.5mm; there is 5mm thick sodium sulfide on both sides of the substrate;

[0066] The cathode is made of stainless steel, with a triangular cross-section and an area of ​​600 cm 2 , thickness is 2mm;

[0067] (2) inserting 300 anodes and 301 cathodes into a closed electrolytic cell with the anodes and cathodes spaced apart;

[0068] The electrolyte is 80% acetonitrile and 20% tetrahydrofuran as solvent, the electrolyte is 50g / L sodium tetrafluoroborate and 12g / L sodium chloride, the oxidant is 10g / L hydrogen peroxide and 20g / L sodium perchlorate, and there is no additive; the distance between the same electrodes is controlled to be 20mm, the cell voltage is 1.5V, and the current density is 300A / m 2 , the electrolyte temperature is 30℃, the circulation speed is 5L / min, and the power is turned on for electrolysis; when the residual electrode rate of the anode is about 10%, the power is stopped, the anode and cathode are taken out, and the anode and cathode products are peeled off manually; the products enter the subsequent process, and the residual electrode returns to the anode preparation process.

[0069] Example 2: An electrochemical metallurgical method for extracting metal and sulfur from metal sulfides, the specific steps are as follows:

[0070] (1) Preparation of tin sulfide anode by vacuum evaporation: Tin sulfide (SnS) is a product of a chemical plant in Hubei Province, with a tin sulfide content of ≥95% and a tin sulfide particle size of 100 μm. The heating method is resistance heating, and the vacuum degree is maintained at 10- 3 Pa, the substrate is made of stainless steel, the longitudinal section is square, and the longitudinal section area is 180cm 2 , thickness is 1mm, and there is a total of 10mm thick tin sulfide on both sides of the substrate;

[0071] The cathode is made of stainless steel, with a square cross-section and an area of ​​200 cm 2 , thickness is 1.5mm;

[0072] (2) Take 240 anodes and 241 cathodes, and insert the anodes and cathodes into the electrolyte at intervals;

[0073] The electrolyte uses water as solvent, the electrolyte is 55g / L stannous sulfate, 50g / L sulfuric acid, the oxidant is 20g / L ferric chloride, the additive is 25mg / L cresol sulfonic acid, the distance between the electrodes is controlled to be 22mm, the cell voltage is 2.5V, and the current density is 220A / m 2 , the electrolyte temperature is 50℃, the circulation speed is 15L / min, and the power is turned on for electrolysis. When the residual electrode rate of the anode is about 5%, the power is stopped; the cathode and cathode are taken out, the electrolyte in the electrolytic cell is drained, and the cathode and cathode products are mechanically stripped; the products enter the subsequent process, and the residual electrode returns to the anode preparation process.

[0074] Example 3: An electrochemical metallurgical method for extracting metal and sulfur from metal sulfides, the specific steps are as follows:

[0075] (1) Aluminum sulfide anode was prepared by magnetron sputtering: Aluminum sulfide (Al2S3) was a product of a chemical plant in Hubei Province, with an aluminum sulfide content of ≥95%. The target material was aluminum sulfide target, and the vacuum degree after filling with argon was 1Pa. The substrate was made of titanium alloy, with a square longitudinal section and a longitudinal section area of ​​800cm. 2 , thickness is 2mm, and there is 3mm thick aluminum sulfide on both sides of the substrate;

[0076] The cathode is made of stainless steel, with a square cross-section and an area of ​​0.1 m 2 , thickness is 2.5mm;

[0077] (2) Take 350 anodes and 351 cathodes, and insert the anodes and cathodes into the electrolyte at intervals.

[0078] The electrolyte is 80% methanol and 20% acetonitrile as solvent, the electrolyte is 60g / L aluminum chloride and 10g / L ammonium chloride, the oxidant is 20g / L hydrogen peroxide, and there is no additive; the distance between the electrodes is controlled to be 18mm, the cell voltage is 1.9V, and the current density is 280A / m 2The electrolyte temperature is 25°C, the circulation speed is 7L / min, and the electrolysis is powered on. When the residual electrode rate of the anode is about 10%, the power is stopped, the anode and cathode are taken out, and the products are peeled off manually. The products enter the subsequent process, and the residual electrode returns to the anode preparation process.

[0079] Example 4: An electrochemical metallurgical method for extracting metal and sulfur from metal sulfides, the specific steps are as follows:

[0080] (1) Antimony sulfide anodes were prepared by chemical vapor deposition: antimony powder was a product of an antimony smelter in Shandong, and its antimony content was ≥90%; sulfur powder was a product of a chemical plant in Yunnan, and its sulfur content was ≥90%. The sulfur powder was placed in the low-temperature zone of an evaporation container, and the antimony powder was placed in the high-temperature zone. Argon gas was filled into the equipment, and the sulfur powder was heated to volatilize, and react with the antimony powder to generate antimony sulfide. The temperature was controlled to volatilize the antimony sulfide and deposit it on a substrate; the substrate was made of lead alloy, and its longitudinal section was circular with a longitudinal section area of ​​200 cm 2 , thickness is 1mm, and there is 6mm thick antimony sulfide on both sides of the substrate;

[0081] The cathode is made of titanium, with a circular longitudinal section and an area of ​​240 cm 2 , thickness is 1.5mm;

[0082] (2) Take 270 anodes and 271 cathodes, and insert the anodes and cathodes into the electrolyte at intervals;

[0083] The electrolyte uses water as solvent, the electrolyte is 60g / L sodium sulfide, 30g / L sodium hydroxide, 15g / L sodium sulfide, the oxidant is 20g / L sodium hypochlorite, there is no additive, the distance between the same electrodes is controlled to be 25mm, the cell voltage is 2.7V, and the current density is 350A / m 2 The electrolyte temperature is 60°C and the circulation speed is 10L / min. During the electrolysis process, ultrasonic method is used to strip sulfur from the surface of the anode and power is turned on for electrolysis. When the residual electrode rate of the anode is about 15%, the power is stopped, the anode and cathode are taken out, the electrolyte in the electrolytic cell is drained, the cathode product is stripped manually, and the anode product is recovered in the electrolytic cell. The product enters the subsequent process, and the residual electrode returns to the anode preparation process.

[0084] Example 5: An electrochemical metallurgical method for extracting metal and sulfur from metal sulfides, the specific steps are as follows:

[0085] The bismuth sulphate concentrate in this embodiment was taken from a bismuth smelter in Hunan Province. Its chemical composition is shown in Table 1:

[0086] Table 1 Chemical composition mass fraction (%) of bismuth sulfide concentrate from a bismuth smelter in Hunan

[0087]

[0088] (1) crushing bismuthinite concentrate, mixing it evenly with 0.5% of the concentrate weight of stainless steel fiber, heating and melting it in a vacuum induction furnace, and casting it into an anode plate by sand casting method, with the size of 1000 mm in length, 550 mm in width, and 55 mm in thickness;

[0089] The cathode is made of copper, with a square cross-section and an area of ​​0.55 m 2 , thickness is 5mm;

[0090] (2) Take 40 anodes and 41 cathodes and insert them into the electrolyte.

[0091] The electrolyte uses water as solvent, the electrolyte is 180g / L bismuth chloride, 150g / L hydrochloric acid, the oxidant is 25g / L ferric sulfate, and there is no additive; the distance between the same electrodes is controlled to be 120mm, the cell voltage is 3.1V, and the current density is 200A / m 2 The electrolyte temperature is 45°C, the circulation speed is 10L / min, and the power is turned on for electrolysis. When the residual electrode rate of the anode is about 10%, the power is stopped, the anode and cathode are taken out, and the anode and cathode products are peeled off by ultrasonic method; the products enter the subsequent process, and the residual electrode returns to the anode preparation process.

[0092] Example 6: An electrochemical metallurgical method for extracting metal and sulfur from metal sulfides, the specific steps are as follows:

[0093] (1) The anode is prepared by a centrifugal forming method: the bismuthinite concentrate is crushed to a particle size of 100 μm, sulfur powder is selected as a forming agent, 1% of the mass of the concentrate of carbon fiber is added, mixed evenly, and loaded into a centrifuge mold, the speed is adjusted to 3500 r / min, and the size of the green body is 850 mm long, 650 mm wide, and 60 mm thick; the green body is sent to a sintering process, and the sintering temperature is adjusted to 750° C. in a nitrogen atmosphere, and kept warm for 2 hours;

[0094] The cathode material is titanium, the longitudinal section shape is square, and the longitudinal section area is 0.6m 2 , thickness is 6mm;

[0095] (2) Take 35 anodes and 36 cathodes, and insert the anodes and cathodes into the electrolyte at intervals;

[0096] The electrolyte uses water as solvent, the electrolyte is 240g / L bismuth fluoride silicate, 150g / L fluoride silicate and 30g / L sodium chloride, the oxidant is 20g / L hydrogen peroxide, and there is no additive; the distance between the same electrodes is controlled to be 75mm, the cell voltage is 3.0V, and the current density is 150A / m 2 , the electrolyte temperature is 40°C, the circulation speed is 8L / min, and the power is turned on for electrolysis; when the residual electrode rate of the anode is about 8%, the power is stopped, the anode and cathode are taken out, and the anode and cathode products are peeled off mechanically; the products enter the subsequent process, and the residual electrode returns to the anode preparation process.

[0097] Example 7: An electrochemical metallurgical method for extracting metal and sulfur from metal sulfides, the specific steps are as follows:

[0098] The sulphur manganese ore concentrate in this example is the raw material of a manganese smelter in Yunnan, and its chemical composition is shown in Table 2:

[0099] Table 2 Chemical composition mass fraction of sulphur manganese ore concentrate of a manganese smelter in Yunnan (%)

[0100]

[0101] (1) crushing the sulfide manganese ore concentrate, mixing it evenly with 0.8% of the concentrate weight of carbon fiber, loading it into a vacuum arc furnace for heating and melting, and preparing an anode by a sand casting method. The prepared anode has a size of 1200 mm in length, 500 mm in width, and 40 mm in thickness;

[0102] The cathode material is titanium, the longitudinal section shape is square, and the longitudinal section area is 0.6m 2 , thickness is 6mm;

[0103] (2) Take 45 anodes and 46 cathodes, and insert the anodes and cathodes into the electrolyte at intervals.

[0104] The electrolyte uses water as solvent, the electrolyte is 40g / L manganese chloride, 10g / L hydrochloric acid, 30g / L ammonium chloride, the oxidant is 40g / L potassium permanganate, and there is no additive; the distance between the same electrodes is controlled to be 75mm, the cell voltage is 2.3V, and the current density is 350A / m 2 , the electrolyte temperature is 50℃, the circulation speed is 20L / min, and the electrolysis is powered on; during the electrolysis process, the ultrasonic method is used to strip the sulfur on the surface of the anode. When the residual electrode rate of the anode is about 13%, the power is stopped; the anode and cathode are taken out, the electrolyte in the electrolytic cell is emptied, the cathode product is stripped by mechanical method, and the anode product is manually recovered; the product enters the subsequent process, and the residual electrode returns to the anode preparation process.

[0105] Example 8: An electrochemical metallurgical method for extracting metal and sulfur from metal sulfides, the specific steps are as follows:

[0106] (1) The anode is prepared by a press method: the sulfide manganese ore concentrate is crushed to a particle size of 120 μm, sulfur powder is used as a forming agent, and 1% of the concentrate mass of stainless steel fiber is added. After mixing evenly, the mixture is loaded into a mold of a press machine and pressed under a pressure of 25 MPa. The pressing speed is 12 mm / s, and the holding time is 1.5 h. The size of the green body is 1000 mm long, 600 mm wide, and 50 mm thick. The green body is sent to a sintering process. Under a nitrogen atmosphere, the sintering temperature is adjusted to 1200° C. and kept at this temperature for 1.5 h.

[0107] The cathode is made of stainless steel, with a square longitudinal section and an area of ​​0.6 m 2 , thickness is 4mm;

[0108] (2) Take 40 anodes and 41 cathodes, and insert the anodes and cathodes into the electrolyte at intervals.

[0109] The electrolyte uses water as solvent, the electrolyte is 45g / L manganese chloride, 80g / L ammonium sulfate, 10g / L hydrochloric acid, the oxidant is 20g / L hydrogen peroxide, and there is no additive; the distance between the same electrodes is controlled to be 70mm, the cell voltage is 2.0V, and the current density is 400A / m 2 The electrolyte temperature is 45°C, the circulation speed is 21L / min, and the electrolysis is carried out. When the residual electrode rate of the anode is about 15%, the power is stopped, the anode and cathode are taken out, and the anode and cathode products are peeled off by ultrasonic method; the products enter the subsequent process, and the residual electrode returns to the anode preparation process.

[0110] Example 9: An electrochemical metallurgical method for extracting metal and sulfur from metal sulfides, the specific steps are as follows:

[0111] The sphalerite concentrate in this example is the raw material of a zinc smelter in Yunnan, and its chemical composition is shown in Table 3:

[0112] Table 3 Chemical composition mass fraction of sphalerite concentrate from a zinc smelter in Yunnan (%)

[0113]

[0114] (1) The anode is prepared by hot-dip plating: Sphalerite concentrate and 15% copper, 8% sulfur, and 10% tin by mass of the concentrate are added to a vacuum induction furnace and heated to melt. The substrate is made of lead alloy and has a fence-like longitudinal cross-sectional shape with a longitudinal cross-sectional area of ​​0.25 m 2 , with a thickness of 3mm. After a layer of carbon fiber is coated on the surface of the substrate, it is inserted into the melt for hot-dip coating. After hot-dip coating, there is a total of 15mm thick sphalerite concentrate on both sides of the substrate.

[0115] The cathode is made of aluminum, with a square cross-section and an area of ​​0.25 m 2 , thickness is 3mm;

[0116] (2) Take 150 anodes and 151 cathodes, and insert the anodes and cathodes into the electrolyte at intervals.

[0117] The electrolyte uses water as solvent, the electrolyte is 180g / L zinc sulfate, 120g / L sulfuric acid, the oxidant is 40g / L ferric chloride, the additive is 10mg / L gelatin, the distance between the electrodes is controlled to be 30mm, the cell voltage is 2.7V, and the current density is 450A / m 2The electrolyte temperature is 45°C, the circulation speed is 22L / min, and the electrolysis is carried out. When the residual electrode rate of the anode is about 8%, the power is stopped, the anode and cathode are taken out, and the anode and cathode products are peeled off mechanically; the products enter the subsequent process, and the residual electrode returns to the anode preparation process.

[0118] Example 10: An electrochemical metallurgical method for extracting metal and sulfur from metal sulfides, the specific steps are as follows:

[0119] (1) The anode is prepared by centrifugal molding: the sphalerite concentrate is crushed to a particle size of 90 μm, graphite powder is used as a forming agent, and 10% of copper by mass of the concentrate is added and mixed evenly, and then loaded into a centrifuge mold, and the speed is adjusted to 3300 r / min; the size of the green body is 820 mm long, 680 mm wide, and 60 mm thick; the green body is sent to the sintering process, and the sintering temperature is adjusted to 1150° C. in a nitrogen atmosphere, and the temperature is kept for 1.8 hours;

[0120] The cathode is made of stainless steel, with a square longitudinal section and an area of ​​0.6 m 2 , thickness is 3mm;

[0121] (2) Take 35 anodes and 36 cathodes, and insert the anodes and cathodes into the electrolyte at intervals;

[0122] The electrolyte uses water as solvent, the electrolyte is 100g / L zinc chloride, 80g / L hydrochloric acid, the oxidant is 35g / L potassium permanganate, and the additive is 15mg / L bone glue; the distance between the same electrodes is controlled to be 75mm, the cell voltage is 2.5V, and the current density is 350A / m 2 , the electrolyte temperature is 50℃, the circulation speed is 25L / min, and the power is turned on for electrolysis; when the residual electrode rate of the anode is about 10%, the power is stopped, and the anode product is stripped mechanically during the electrolysis process. After the electrolysis is completed, the anode and cathode are taken out, and the cathode product is stripped by ultrasound; the product enters the subsequent process, and the residual electrode returns to the anode preparation process.

[0123] Example 11: An electrochemical metallurgical method for extracting metal and sulfur from metal sulfides, the specific steps are as follows:

[0124] The galena concentrate in this example is the raw material of a lead smelter in Yunnan, and its chemical composition is shown in Table 4:

[0125] Table 4 Chemical composition mass fraction of galena concentrate from a lead smelter in Yunnan (%)

[0126]

[0127] (1) galena concentrate is heated and melted in a vacuum induction furnace, and an anode is prepared by a full mold casting method. The prepared anode has a size of 910 mm in length, 590 mm in width, and 55 mm in thickness;

[0128] The cathode material is lead, the longitudinal section shape is square, and the longitudinal section area is 0.55m 2 , thickness is 3mm;

[0129] (2) Take 40 anodes and 41 cathodes and insert them into the electrolyte;

[0130] The electrolyte uses water as solvent, the electrolyte is 80g / L lead chloride, 25g / L hydrochloric acid, the oxidant is 30g / L ferric chloride, and the additive is 10mg / L sodium lignosulfonate; the distance between the same electrodes is controlled to be 80mm, the cell voltage is 2.9V, and the current density is 200A / m 2 , the electrolyte temperature is 50°C, the circulation speed is 20L / min, and the power is turned on for electrolysis; when the residual electrode rate of the anode is about 20%, the power is stopped, the anode and cathode are taken out, and the anode and cathode products are recovered by mechanical methods; the products enter the subsequent process, and the residual electrode returns to the anode preparation process.

[0131] Example 12: An electrochemical metallurgical method for extracting metal and sulfur from metal sulfides, the specific steps are as follows:

[0132] (1) The anode is prepared by a press method: the galena concentrate is crushed to a particle size of 150 μm, the forming agent is sulfur powder, the mixture is evenly mixed, and then loaded into a mold of a press machine, and pressed under a pressure of 20 MPa. The pressing speed is 10 mm / s, and the holding time is 2 h. The size of the green body is 800 mm long, 700 mm wide, and 60 mm thick. The green body is sent to a sintering process. Under a nitrogen atmosphere, the sintering temperature is adjusted to 800 ° C and kept at this temperature for 2 h.

[0133] The cathode material is titanium, the longitudinal section shape is square, and the longitudinal section area is 0.6m 2 , thickness is 3.5mm;

[0134] (2) Take 35 anodes and 36 cathodes, and insert the anodes and cathodes into the electrolyte at intervals.

[0135] The electrolyte uses water as solvent, the electrolyte is 100g / L lead fluorosilicate, 60g / L silicic acid, 20g / L sodium chloride, the oxidant is 0.15L / min ozone, and the additive is 10mg / L β-phenol; the distance between the same electrodes is controlled to be 85mm, the cell voltage is 3.1V, and the current density is 240A / m 2 , the electrolyte temperature is 45°C, the circulation speed is 15L / min, and the power is turned on for electrolysis; when the residual electrode rate of the anode is about 15%, the power is stopped, the anode and cathode are taken out, and the anode and cathode products are recovered by ultrasonic method; the products enter the subsequent process, and the residual electrode returns to the anode preparation process.

[0136] Example 13: An electrochemical metallurgical method for extracting metal and sulfur from metal sulfides, the specific steps are as follows:

[0137] The copper matte in this embodiment is the raw material of a copper smelter in Yunnan, and its chemical composition is shown in Table 5:

[0138] Table 5 Chemical composition mass fraction of copper matte from a copper smelter in Yunnan (%)

[0139]

[0140] (1) The anode is prepared by hot-dip plating: copper matte is added to an induction furnace for heating and melting, and a substrate is inserted into the melt for hot-dip plating. The substrate is made of conductive fiber, with a porous longitudinal cross-sectional shape and a longitudinal cross-sectional area of ​​0.35 m 2 , thickness is 3mm, and there is a total of 20mm thick copper matte on both sides of the substrate;

[0141] The cathode is made of stainless steel, with a square longitudinal section and an area of ​​0.4m 2 , thickness is 2mm;

[0142] (2) Take 135 anodes and 136 cathodes, and insert the anodes and cathodes into the electrolyte at intervals.

[0143] The electrolyte uses water as solvent, the electrolyte is 50g / L copper sulfate, 100g / L sulfuric acid and 40g / L sodium chloride, the oxidant is 45g / L iron sulfate, the additives are 15mg / L bone glue, 10mg / L thiourea and 15mg / L casein; the distance between the same electrodes is controlled to be 35mm, the cell voltage is 3.2V, and the current density is 240A / m 2 , the electrolyte temperature is 55°C, the circulation speed is 25L / min, and the power is turned on for electrolysis; when the residual electrode rate of the anode is about 10%, the power is stopped, the anode and cathode are taken out, and the anode and cathode products are recovered by manual methods. The products enter the subsequent process, and the residual electrode returns to the anode preparation process.

[0144] The cyclic voltammetry curve of the copper matte in the above electrolyte is shown in Figure 2 As shown in the figure, there is a very obvious oxidation peak near 3.2V, which corresponds to the oxidation of sulfur in matte. It can be seen that the electrochemical metallurgical method of extracting metal and sulfur from metal sulfides is theoretically feasible. The morphology of the cathode product copper under the scanning electron microscope is shown in Figure 3 , the chemical composition of the corresponding cathode product copper is shown in Table 6;

[0145] Table 6 Chemical composition of cathode product copper (%)

[0146]

[0147] The Raman diagram of the anode product sulfur is shown in Figure 4 And XRD pattern see Figure 5 , the chemical composition of the corresponding anode product sulfur is shown in Table 7;

[0148] Table 7 Chemical composition of sulfur in anode product (%)

[0149]

[0150] It can be seen from the above chart that the purity of copper and sulfur is relatively high, which shows that the electrochemical metallurgical method of extracting metal and sulfur from metal sulfides can be applied to actual production.

[0151] Example 14: An electrochemical metallurgical method for extracting metal and sulfur from metal sulfides, the specific steps are as follows:

[0152] (1) copper matte and 5% copper by mass of the copper matte are placed in a reverberatory furnace for heating and melting, and the liquid copper matte is cast into an anode plate by a sand casting method. The dimensions after preparation are 1000 mm in length, 500 mm in width, and 50 mm in thickness;

[0153] The cathode is made of copper, with a square cross-section and an area of ​​0.5 m 2 , thickness is 5mm;

[0154] (2) Take 45 anodes and 46 cathodes, and insert the anodes and cathodes into the electrolyte at intervals.

[0155] The electrolyte uses water as solvent, the electrolyte is 45g / L copper chloride and 180g / L hydrochloric acid, the oxidant is 0.1L / min oxygen, the additives are 30mg / L gelatin and 8mg / L thiourea; the distance between the electrodes is controlled to be 90mm, the cell voltage is 3.5V, and the current density is 280A / m 2 , the electrolyte temperature is 60℃, the circulation speed is 30L / min, and the power is turned on for electrolysis; when the residual electrode rate of the anode is about 20%, the power is stopped, the anode and cathode are taken out, and the anode and cathode products are recovered by mechanical methods; the products enter the subsequent process, and the residual electrode returns to the anode preparation process.

[0156] The specific implementation modes of the present invention are described in detail above, but the present invention is not limited to the above implementation modes, and various changes can be made within the knowledge scope of ordinary technicians in this field without departing from the purpose of the present invention.

Claims

1. An electrochemical metallurgical method for extracting metal and sulfur from metal sulfides, characterized in that: The specific steps are as follows: (1) preparing a metal sulfide into an electrode, i.e., a metal sulfide electrode, and adjusting the semiconductor type of the metal sulfide electrode to be p-type; in the preparation process, adjusting the metal sulfide composition by adding elements, and adjusting the mechanical properties by adding a reinforcing agent; wherein the added elements are one or more of copper, manganese, cobalt, sulfur, molybdenum, tin, bismuth, lead, zinc, selenium, antimony, tellurium, and cadmium, and the reinforcing agent is carbon fiber, stainless steel fiber, copper fiber, or lead fiber; (2) Using a metal sulfide electrode as an anode, inserting the anode and cathode into an electrolyte at intervals to form an electrode array for electrolysis, wherein the sulfur element in the metal sulfide is oxidized and adsorbed on the anode in the form of sulfur element, and the metal ions enter the electrolyte and undergo a reduction reaction on the cathode surface to generate metal element, wherein the cathode is titanium, copper, stainless steel, lead, zinc, aluminum or graphite; the electrolyte contains a solvent, an electrolyte, an oxidant, and an additive, wherein the solvent is water or an organic solvent, and the organic solvent is one or more of anhydrous acetic acid, methanol, acetonitrile, and tetrahydrofuran; The oxidant is one or more of ferric chloride, potassium permanganate, oxygen, hydrogen peroxide, fluorine, ozone, ferric sulfate, chlorine, bromine vapor, sodium dichromate. When the oxidant is a gas, the flow rate is 0.01 to 5 L / min. When the oxidant is a non-gas, the content of the oxidant in the electrolyte is 0.1 to 1000 g / L. The additive is one or more of gelatin, bone glue, hide glue, thiourea, β-phenol, powder glue, sodium wood sulfonate, carbolic acid, tannin, diphenylamine, phenol, borax, and casein, and the content of the additive in the electrolyte is 0 to 1000 g / L; The distance between the same plates is 1 to 1000 mm, the cell voltage range is 0.1 to 10 V, and the current density control range is 1 to 1000 A / m 2 , the electrolyte temperature range is 25-100°C, the circulation speed range is 1-100L / min, and the anode residual rate is 1%-25%.

2. The electrochemical metallurgical method for extracting metal and sulfur from metal sulfides according to claim 1, characterized in that: The metal sulfide is a pure substance or a mixture. The pure substance includes but is not limited to lithium sulfide, sodium sulfide, magnesium sulfide, aluminum sulfide, potassium sulfide, calcium sulfide, manganese sulfide, iron sulfide, ferrous sulfide, cobalt sulfide, copper sulfide, cuprous sulfide, zinc sulfide, molybdenum sulfide, silver sulfide, cadmium sulfide, stannous sulfide, antimony sulfide, lead sulfide, and bismuth sulfide; the mixture is a natural sulfide concentrate, a metallurgical intermediate or by-product. The natural sulfide concentrate includes but is not limited to pyrite, chlorovanadate, chalcopyrite, bornite, chalcocite, covellite, chalcopyrite, tetrahedrite, tetrahedrite, sulfur Arsenic copper ore, sulfide copper cobalt ore, sulfide cobalt ore, arsenic cobalt ore, tungsten ore, sulfide tin ore, stannite, cylindrical tin ore, sulfide tin lead ore, stibnite tin lead ore, disulfide tin ore, rhombic sulfide tin ore, sulfide manganese ore, molybdenite, iron molybdenite, sulfide molybdenite, sphalerite, wurtzite, galena, sulfide antimonite, wheel ore, bismuthinite, sulfide bismuth tellurite, brittle sulfide bismuth ore, sulfide bismuth selenite, sulfide copper bismuth ore, chalcocite bismuth ore, stibnite, brittle sulfide lead antimonite, antimony tetrahedrite; metallurgical intermediates or by-products include but are not limited to copper matte, cobalt matte, lead copper matte, antimony matte, iron matte, copper molybdenum matte, bismuth matte.

3. The electrochemical metallurgical method for extracting metal and sulfur from metal sulfides according to claim 2, characterized in that: The preparation method of the metal sulfide electrode is thermal spraying, hot plating, physical vapor deposition, chemical vapor deposition, casting or powder metallurgy. The physical vapor deposition method includes but is not limited to vacuum evaporation and magnetron sputtering; the casting method includes but is not limited to sand casting and full mold casting; the powder metallurgy method includes but is not limited to press method and centrifugal forming method.

4. The electrochemical metallurgical method for extracting metal and sulfur from metal sulfides according to claim 3, characterized in that: Thermal spraying method: using a heat source to melt the metal sulfide powder, spraying it onto the surface of the substrate by controlling the pressure of the protective gas to form a metal sulfide electrode, wherein the pressure is 1-20 MPa; Vacuum evaporation method: Add metal sulfide powder into the evaporation container, adjust the vacuum degree, and heat to deposit the powder on the substrate to obtain the metal sulfide electrode. The vacuum degree is 10 -6 ~10 2 Pa; Magnetron sputtering method: connect the substrate to the anode, connect the metal sulfide target to the cathode, and evacuate to 10 -3 Pa, fill with argon to maintain the vacuum degree at 10 -2 In the range of 10 Pa to 10 Pa, power is supplied, and metal sulfide electrodes are obtained by magnetron sputtering, wherein the material of the sulfide target includes but is not limited to magnesium sulfide, zinc sulfide, calcium sulfide, aluminum sulfide, and cadmium sulfide; Chemical vapor deposition method: A protective gas is filled into the chemical vapor deposition device, metal powder and sulfur powder are placed in an evaporator, and the metal powder and sulfur powder are heated to evaporate and enter the reaction chamber for reaction, and then deposited on the substrate to obtain a metal sulfide electrode; Hot-dip method: Use a smelting furnace to melt the metal sulfide, insert the substrate into the liquid metal sulfide for hot-dip to obtain a metal sulfide electrode; Sand casting method: Use molding sand and core sand to prepare a mold cavity, melt the metal sulfide in a smelting furnace, pour it into the mold cavity, cool and solidify, and obtain the metal sulfide electrode by sand dropping and cleaning; Full-mold casting method: bury the foam plastic in sand, melt the metal sulfide in a smelting furnace, replace the foam plastic with the metal sulfide melt, cool and solidify, and obtain the metal sulfide electrode by sand dropping and cleaning; Press method: the metal sulfide powder and the forming agent are mixed evenly and then loaded into a mold, and pressed to obtain a green body, and the green body is sintered to obtain a metal sulfide electrode, wherein the pressing pressure is 10-30 MPa, the pressing speed is 1-15 mm / s, and the holding time is 0.1-10 h; Centrifugal forming method: the metal sulfide powder and the forming agent are mixed evenly and then loaded into a mold, and the green body is obtained by centrifugal forming, and the green body is sintered to obtain a metal sulfide electrode, wherein the speed of the centrifugal forming is 500-4500r / min; The sintering atmosphere is a protective gas atmosphere, the temperature is 400-1200° C., and the sintering time is 0.1-10 hours; Protective gases include, but are not limited to, argon, nitrogen, and carbon dioxide.

5. The electrochemical metallurgical method for extracting metal and sulfur from metal sulfides according to claim 4, characterized in that: The average particle size of the metal sulfide powder is 1 nm to 1 mm.

6. The electrochemical metallurgical method for extracting metal and sulfur from metal sulfides according to claim 4, characterized in that: The material of the substrate is metal, graphite or composite material. The material of the metal substrate includes but is not limited to copper, zinc, lead, tin, aluminum, titanium, stainless steel, aluminum alloy, lead alloy, titanium alloy, manganese alloy, copper alloy, zinc alloy, tin alloy, tungsten alloy, and molybdenum alloy. The material of the composite substrate includes but is not limited to conductive silicone rubber, conductive plastic, and conductive fiber.

7. The electrochemical metallurgical method for extracting metal and sulfur from metal sulfides according to claim 4, characterized in that: The longitudinal cross-sectional area of ​​the substrate is 1 cm 2 ~10m 2 , thickness or radius is 1 to 2000 mm, and the adhesion thickness of metal sulfide on the substrate is 1 to 30 mm.

8. The electrochemical metallurgical method for extracting metal and sulfur from metal sulfides according to claim 4, characterized in that: Forming agents include, but are not limited to, starch, sulfur, molybdenum disulfide, graphite powder, paraffin, and rosin.

9. The electrochemical metallurgical method for extracting metal and sulfur from metal sulfides according to claim 1, characterized in that: The electrolyte is one or more of sulfuric acid, perchloric acid, hydrobromic acid, hydrochloric acid, silicic acid, carbonic acid, phosphoric acid, nitrous acid, hydroiodic acid, tartaric acid, oxalic acid, citric acid, hydrofluoric acid, acetic acid, hypochlorous acid, boric acid, bismuth chloride, bismuth sulfate, bismuth fluorosilicate, sodium chloride, lithium perchlorate, magnesium perchlorate, molybdenum chloride, sodium sulfate, aluminum chloride, sodium nitrate, molybdenum sulfate, copper chloride, copper sulfate, lead chloride, lead fluorosilicate, cadmium chloride, antimony chloride, silver nitrate, stannous sulfate, zinc chloride, sodium acetate, sodium nitrite, sodium borate, zinc sulfate, manganese chloride, cobalt chloride, ammonium sulfate, cobalt sulfate, sodium oxalate, sodium tetrafluoroborate, sodium sulfide, sodium hydroxide, calcium sulfonate, potassium methoxide, aluminum stearate, ammonium chloride, and tetraethylammonium tetrafluoroborate; the electrolyte content in the electrolyte is 0.1-1000 g / L.

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