WO2023246367A1 - Antimony-sulfide-containing ore-based molten salt electrolysis continuous production method and apparatus - Google Patents

Antimony-sulfide-containing ore-based molten salt electrolysis continuous production method and apparatus Download PDF

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WO2023246367A1
WO2023246367A1 PCT/CN2023/093924 CN2023093924W WO2023246367A1 WO 2023246367 A1 WO2023246367 A1 WO 2023246367A1 CN 2023093924 W CN2023093924 W CN 2023093924W WO 2023246367 A1 WO2023246367 A1 WO 2023246367A1
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antimony
electrolysis
furnace
molten salt
electrolytic
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French (fr)
Chinese (zh)
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杨建广
朱强
丁瑞泽
唐朝波
南天翔
曾伟志
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中南大学
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/34—Electrolytic production, recovery or refining of metals by electrolysis of melts of metals not provided for in groups C25C3/02 - C25C3/32
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/06—Operating or servicing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the invention relates to a method and device for the continuous electrolysis production of molten salt containing antimony sulfide ore, and belongs to the technical field of non-ferrous metal metallurgy.
  • Antimony is a rare strategic metal widely used in flame retardant, alloys, ceramics, pigments, semiconductors and chemical industries.
  • the raw material for antimony smelting in China is mainly antimony ore (Sb 2 S 3 ).
  • antimony smelting enterprises mainly use the "blast furnace volatilization-reverberatory furnace reduction smelting" process to produce metallic antimony. That is, after the antimony is granulated, it is added to the blast furnace together with coke and flux for volatilization and smelting, so that the antimony enters the high-temperature flue gas and is recovered in the form of crude antimony oxide after condensation and dust collection.
  • the low-concentration SO 2 generated during the smelting process is desulfurized and discharged null.
  • Blast furnace volatilization smelting has the advantages of strong raw material adaptability, large processing capacity, high metal recovery rate, easy mechanical operation, and low labor intensity. Since the successful research of the Yuan Tin Mine Bureau, it has developed rapidly in our country and has now become a major Antimony smelting method. However, the special operating conditions of "low material column, thin material layer, high coke rate, and high temperature furnace top" determine that this process has the disadvantages of high coke rate, high energy consumption, short furnace life, and complicated flue gas cooling and dust collection systems.
  • the purpose of the present invention is to provide a method for the continuous electrolysis production of molten salts containing antimony sulfide ores, using two electrolytic furnaces to smelt antimony in sections, so as to solve the problem of the current single electrolytic furnace, namely patents 201710775124.0 and 202010114724.4.
  • the above-mentioned antimony sulfide-containing ore molten salt electrolysis antimony refining method cannot achieve continuous production in the true sense.
  • the current efficiency is low, the electrolysis energy consumption is high, the electrolysis process parameters are difficult to control in real time, and the antimony content in the residue is high.
  • a method for continuous electrolysis production of antimony sulfide ore molten salt including the following steps:
  • step (2) Enter the electrolyzed melt obtained in step (1) through the chute into the depletion electrolytic furnace for constant voltage depletion electrolysis. Before electrolysis, replenish molten salt, metallic antimony liquid and elemental sulfur to discharge antimony from the depletion electrolytic furnace respectively.
  • the flue gas port of the depleted electrolytic furnace is discharged, and the depleted slag is released from the slag discharge port.
  • the mass percentage of antimony sulfide ore and eutectic molten salt is 10:1 to 5:4, preferably 6:1 to 5:2.
  • the eutectic molten salt is a mixture of sodium chloride and potassium chloride, and the mass percentage of sodium chloride and potassium chloride is 7:3-2:7, preferably 4:5-2:5.
  • step (1) the temperature in the high antimony electrolysis furnace is 700-950°C, and the heating rate is 8-15°C/min, preferably 850-900°C.
  • the anode current density during electrolytic smelting is 1000-5000 A ⁇ m -2 , preferably 2000-3000 A ⁇ m -2 ; the cell voltage is controlled below 4 V, preferably 3.8 V or less; the distance between anode and cathode is 1 to 8cm, preferably 2 to 4cm.
  • the inert gas is preferably nitrogen or argon, the pressure of the inert gas blown is 0.12-0.35MPa, and the inert gas flow rate is 40-1100 L/(min ⁇ m 3 ).
  • the inert gas needs to be preheated before blowing in.
  • the preferred temperature of the preheated gas is 700 to 950°C.
  • Preheating the inert gas can prevent the local temperature in the high antimony electrolysis furnace from being too cold, resulting in insufficient melt temperature and affecting the electrolysis efficiency.
  • the electrolytic smelting reaction time is 2 to 20 hours, preferably 8 to 15 hours.
  • the high antimony electrolysis furnace adopts the electrolysis method of constant current limiting voltage and inert gas blowing to stir the molten salt, and replenishing materials according to the theoretical consumption, including electrolysis consumption and volatilization loss.
  • the replenishing materials are antimony sulfide ore, chlorine A mixture of sodium chloride and potassium chloride.
  • the material concentration in the electrolysis furnace can be maintained sufficient, uniform and stable.
  • step (2) the molten salt supplemented before the depletion electrolysis is eutectic molten salt, and the molten salt supplementary amount is 5 to 40% (5 to 40% based on the melt coming out of the high antimony electrolysis furnace). %).
  • Supplementing molten salt before electrolysis can reduce the viscosity value of the melt coming out of the high antimony electrolysis furnace, reduce the energy consumption loss in the electrolysis process and facilitate the subsequent discharge of depleted slag.
  • Results of current efficiency and energy consumption based on experiments with different amounts of molten salt supplementation. Determine the amount of molten salt to replenish.
  • step (2) the temperature in the depletion electrolysis furnace is 700-1050°C, and the heating rate is 8-15°C/min, preferably 850-950°C.
  • the temperature in the depleted electrolytic furnace is higher than the temperature in the high antimony electrolytic furnace. Since the higher the temperature, the smaller the viscosity of the melt. Increasing the temperature and supplementing molten salt are both to reduce the viscosity of the melt in the depleted electrolytic bath, so as to improve The current efficiency of the electrolysis process and the reduction of electrolysis energy consumption.
  • step (2) the cell voltage during depletion electrolysis is 1.5-4.5 V, preferably 2.5-3.5 V; the distance between cathodes and anodes is 1-8 cm, preferably 2-4 cm.
  • the depletion electrolysis reaction time is 2 to 6 hours, preferably 3 to 4 hours; the antimony in the slag discharged from the slag outlet after the depletion electrolysis is ⁇ 1wt.%.
  • the depleted electrolytic furnace uses constant voltage electrolysis to deplete the post-electrolysis melt of the electrolytic high antimony electrolysis furnace, so that the antimony in the final residue reaches a lower level (the antimony in the slag released from the slag outlet after depletion electrolysis ⁇ 1wt.%), and separate the molten salt from the gangue and other components in the mineral to achieve the opening of impurities.
  • two consecutive furnaces are combined into the process of antimony refining by molten salt electrolysis of antimony sulfide ores.
  • the antimony liquid is discharged from the antimony discharge port.
  • the remaining impurities including gangue and unelectrolyzed The antimony sulfide melt enters the depletion electrolytic furnace through the chute.
  • constant voltage depletion electrolysis is performed, so that the antimony in the final discharged residue is at a lower level.
  • the invention creatively performs constant current and voltage limiting electrolysis in the high antimony electrolytic furnace, and performs constant voltage depletion electrolysis in the depleted electrolytic furnace.
  • the antimony content in the residue can be effectively reduced and energy consumption can be saved.
  • the reasons are as follows: Due to the high concentration of antimony in the high-antimony electrolysis furnace, the process of constant current and voltage-limited electrolysis of antimony has high current efficiency and low electrolysis energy consumption. However, if constant current and voltage-limited electrolysis is maintained, the accumulation of impurities will lead to changes in the physical properties of the melt. , the current efficiency decreases and energy consumption increases, so it needs to be transferred to a depleted electrolysis furnace.
  • the molten salt supplement, cell voltage, electrode spacing and electrolysis temperature are controlled within the above ranges respectively.
  • the electrolysis efficiency is the highest and the energy consumption is the lowest. This is due to the molten salt supplement,
  • the increase in temperature can effectively improve the viscosity, conductivity and other physical properties of the molten salt, which is more conducive to the progress of molten salt electrolysis.
  • the constant voltage process can effectively ensure that the current density is controlled according to the concentration of antimony sulfide in the melt during the electrolysis process to avoid excessive waste of electrical energy.
  • Another object of the present invention is to provide a combined molten salt electrolysis furnace device matched with the above-mentioned method for continuous electrolysis production of molten salt containing antimony sulfide ores.
  • the electrolytic furnace includes a hollow furnace body and an electrolysis unit arranged in the furnace body; the furnace body is provided with a feed inlet and a flue gas port respectively in the upper part, and is respectively provided in the lower part.
  • the slag discharge port of the high antimony electrolytic furnace is connected through a chute.
  • the high antimony electrolytic furnace is equipped with a gas lance that extends into the furnace body and blows inert gas.
  • a thermal resistor is provided on the outer wall of the electrolysis furnace, and the thermal resistor is covered with an insulation layer; the chute is equipped with a discharge valve and a sampling observation port, and the flow rate of the melt in the chute is 0.1 to 0.8 m ⁇ s. -1 ;
  • the electrolysis unit includes a cathode arranged at the bottom of the furnace body and an anode arranged at the upper part of the furnace body.
  • the anode is connected to an anode guide rod extending out of the furnace body to connect the positive electrode of the power supply through a wire; the cathode is connected through a wire Connect the negative terminal of the power supply.
  • the gas spray gun and anode guide rod are made of aluminum oxide.
  • the feeder continuously feeds the material and the gas spray gun stirs the melt.
  • the antimony liquid obtained by electrolysis is discharged from the antimony discharge port.
  • the sulfur-containing flue gas is collected from the flue gas port, and the slag is discharged from the slag discharge port.
  • Sampling and analysis are carried out from the sampling observation port of the chute to achieve optimal control of the electrolysis process parameters of the depletion electrolysis furnace.
  • the amount of electrolytic materials obtained from the depleted electrolysis furnace can be controlled and the physical properties of the components can be observed.
  • the melt flow in the chute can be controlled within the above preferred range, which can effectively avoid the loss of melt heat. loss or blockage of the chute.
  • the method and device for the continuous electrolysis production of antimony sulfide ore molten salt of the present invention have the following advantages:
  • the design of the two-furnace molten salt electrolysis antimony smelting of high antimony electrolytic furnace and depleted electrolytic furnace enables the entire electrolysis process to be carried out simultaneously under two different process parameters according to needs, meeting the needs of the molten salt electrolysis process of antimony sulfide materials.
  • the inert gas blows and stirs the constant current electrolysis to achieve high current efficiency, and the static depletion constant voltage electrolysis process realizes the purpose of low antimony content in the molten salt electrolytic slag and the stratification and separation of the molten salt and slag components; fully satisfying the industrial needs Technologically and economically viable requirements for the production process.
  • the present invention realizes the circulation and reuse of inert molten salt through the depletion electrolysis of the melt after electrolysis in the high antimony electrolysis furnace and the separation and purification of components such as gangue, which greatly reduces the cost of antimony sulfide ores.
  • Raw material costs for molten salt electrolysis.
  • the present invention can achieve complete continuous production of one-step antimony smelting, and significantly reduce the pyrometallurgical smelting temperature of antimony concentrate, directly producing It produces metallic antimony and elemental sulfur without SO2 emissions. It has the advantages of low energy consumption and high direct recovery rate of antimony and sulfur. It is of great significance to promote the progress of China's antimony metallurgical technology and energy conservation and emission reduction.
  • Figure 1 is a schematic diagram of the continuous electrolysis production device of molten salt containing antimony sulfide ore according to the present invention (1-feeder, 2-thermal resistor, 3-antimony discharge port, 4-gas spray gun, 5-anode guide rod, 6-height Antimony electrolytic furnace, 7-flue gas port, 8-graphite anode, 9-chute, 10-graphite cathode, 11-sampling observation port, 12-coarse antimony tank, 13-depletion electrolytic furnace, 14-insulation layer, 15- Slag discharge port, 16-DC power supply, 17-slag, 18-antimony sulfide, 19-molten salt, 20-antimony liquid).
  • the two-furnace molten salt electrolysis device in this embodiment uses two electrolytic furnaces with the same structure, in which each electrolytic furnace includes a hollow furnace body and an electrolysis unit arranged in the furnace body.
  • the furnace body is equipped with a feeding port and a flue gas port on the upper part, and an antimony discharging port and a slag discharging port on the lower part.
  • a thermal resistor is provided on the outer wall of the furnace body, and the thermal resistor is covered with an insulation layer. The melt is heated by the thermal resistor.
  • the electrolytic furnaces are used as a high antimony electrolytic furnace, and the slag discharge port of this high antimony electrolytic furnace is positioned higher than the feed port of the other as a depleted electrolytic furnace.
  • the slag discharge port of the high antimony electrolytic furnace is then moved through the chute.
  • the chute Connected to the feed inlet of the depletion electrolysis furnace, the chute is equipped with a discharge valve to start or stop the discharge. It is also equipped with a sampling observation port to facilitate sampling from the chute.
  • the flow rate of the melt in the chute is 0.1 ⁇ 0.8 m ⁇ s -1 .
  • the high antimony electrolysis furnace is also equipped with a gas lance that extends into the furnace body and blows inert gas to stir the molten salt.
  • the antimony liquid obtained by electrolysis is discharged from the antimony discharge port, and the sulfur-containing flue gas is collected from the flue gas port.
  • the slag of the depleted electrolytic furnace is discharged from the slag
  • the electrolysis unit in the furnace body includes a cathode located at the bottom of the furnace body and an anode located at the upper part of the furnace body.
  • the anode is connected to an anode guide rod extending out of the furnace body to connect the positive electrode of the power supply through a wire, and the cathode is directly connected to the power supply through a wire. negative electrode.
  • the chemical composition of antimony sulfide concentrate A is (wt. %): Sb 52.91, S 23.12, Si 7.15, Fe 1.61, As 0.53, Al 1.08, Pb 0.29, Ca 0.33, Mg 0.14.
  • the chemical composition of antimony sulfide concentrate B is (wt. %): Sb 32.56, S 28.12, Si 2.51, Fe 5.61, As 2.53, Al 1.12, Pb 0.45, Ca 0.31, Mg 0.28.
  • Example 2 The same raw materials as in Example 1 above. Weigh the mixture of antimony sulfide and molten salt with a ratio of 6:1, place it in a high antimony electrolytic furnace, turn on the thermal resistor to increase the temperature to 850°C, adjust the electrode spacing to 5cm, and turn on the gas spray gun to control the gas pressure to 0.15MPa , the flow rate is 185 L/(min ⁇ m 3 ). Start the power supply and set the current density to 1800 A ⁇ m -2 and the cell voltage to 4.0V. Continue to add materials according to the theoretical consumption. After 15 hours of electrolysis, the crude antimony is released and the sulfur-containing smoke is collected.
  • the remaining high antimony electrolytic furnace melt passes through The chute enters the depleted electrolytic furnace, and 10% of the molten salt is added (calculated based on the melt coming out of the high antimony electrolytic furnace).
  • the temperature in the electrolytic furnace is controlled at 900°C, and the voltage of the tank is controlled at 2 V when the power is turned on.
  • the current efficiency of the entire electrolysis furnace process is 85.8%, the electrolysis energy consumption is 2.83kWh ⁇ kg -1 , and the electrolysis residue contains 0.95% antimony.
  • This comparative example is a single electrolytic furnace gas agitation constant voltage molten salt electrolysis scheme: the same raw materials as the above-mentioned Example 1, according to the patent "A method and device for molten salt electrolysis of antimony sulfide-containing materials (Chinese Patent 202010114724.4)"
  • the plan is to carry out a molten salt electrolysis test. The difference is that the electrolysis cycle is extended to 12 hours, and the amount of feed during the electrolysis process is the same as in Example 1.
  • the current efficiency was 72.85%
  • the electrolysis energy consumption was 3.65kWh ⁇ kg -1
  • the stratification effect of the slag and molten salt was poor
  • the antimony content in the slag was 2.56%.
  • This comparative example is a single electrolytic furnace non-gas agitation constant voltage molten salt electrolysis scheme: the same raw materials as the above-mentioned Example 1, according to the patent "A low-temperature molten salt electrolysis clean metallurgical method and device (Chinese Patent 201710775124.0)"
  • the plan is to carry out a molten salt electrolysis test.
  • the difference is that the electrolysis cycle is extended to 12 hours, and the amount of feed during the electrolysis process is the same as in Example 1.
  • the current efficiency was 65.23%
  • the electrolysis energy consumption was 3.86kWh ⁇ kg -1
  • the antimony content in the slag was 1.58%.
  • This comparative example is the same electrolysis temperature solution for the high antimony electrolytic furnace and the depleted electrolytic furnace: the same raw materials as in the above example 1, weigh a mixture of antimony sulfide and molten salt with a mass percentage of 5:1, and place it in the high antimony electrolytic furnace in sequence. , turn on the thermal resistor to increase the temperature to 900°C, adjust the electrode spacing to 4cm, turn on the gas spray gun to control the gas pressure to 0.15Mpa, and the flow rate to 185 L/(min ⁇ m 3 ). Start the power supply and set the current density to 2100 A ⁇ m -2 and the cell voltage limit to 3.8V. Continue to replenish materials according to the theoretical consumption.
  • This comparative example uses a constant current scheme for both the high antimony electrolytic furnace and the depleted electrolytic furnace: the same raw materials as in Example 1 above, weigh a mixture of antimony sulfide and molten salt with a mass percentage of 5:1, and place them in the high antimony electrolysis furnace in sequence.
  • the furnace turn on the thermal resistor to increase the temperature to 900°C, adjust the electrode spacing to 4cm, turn on the gas spray gun to control the gas pressure to 0.15Mpa, and the flow rate to 185 L/(min ⁇ m 3 ).

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Abstract

An antimony-sulfide-containing ore-based molten salt electrolysis continuous production method and apparatus. The method comprises: (1) putting antimony sulfide ore and eutectic molten salt in a high-antimony electrolytic furnace for constant-current voltage-limiting heating electrolytic smelting, in the smelting process, blowing an inert gas to stir the melt, and respectively discharging a metal antimony liquid and elemental sulfur from an antimony discharge port of the high-antimony electrolytic furnace and a flue gas port of the high-antimony electrolytic furnace; and (2) feeding the post-electrolysis melt obtained in step (1) into a depletion electrolytic furnace through a chute for constant-voltage dilution electrolysis, supplementing molten salt before the electrolysis, respectively discharging the metal antimony liquid and elemental sulfur from an antimony discharge port of the depletion electrolytic furnace and a flue gas port of the depletion electrolytic furnace, and discharging post-depletion slag from a slag discharge port. According to the design of molten salt electrolysis antimony smelting in two connected furnaces, the whole electrolysis process can be carried out simultaneously under two different process parameters according to requirements, so that the purpose of enabling low antimony content in the molten salt electrolysis slag, and molten salt and slag component separation is achieved, and the economic and feasible requirements of industrial production technology are satisfied.

Description

一种含硫化锑矿熔盐电解连续化生产的方法及装置A method and device for continuous electrolysis production of molten salt containing antimony sulfide ore 技术领域Technical field
本发明涉及一种含硫化锑矿熔盐电解连续化生产的方法及装置，属于有色金属冶金技术领域。The invention relates to a method and device for the continuous electrolysis production of molten salt containing antimony sulfide ore, and belongs to the technical field of non-ferrous metal metallurgy.
背景技术Background technique
锑是一种稀有的战略金属，广泛用于阻燃、合金、陶瓷、颜料、半导体及化工等领域。我国锑的冶炼原料以辉锑矿（Sb 2S 3）为主，目前锑冶炼企业主要采用“鼓风炉挥发-反射炉还原熔炼”工艺生产金属锑。即辉锑矿制粒后与焦炭、熔剂一同加入鼓风炉内进行挥发熔炼，使锑进入高温烟气，通过冷凝收尘后以粗氧化锑的形式回收，熔炼过程产生的低浓度SO 2脱硫后排空。然后，粗氧化锑在反射炉内通过还原熔炼得到金属粗锑。鼓风炉挥发熔炼具有原料适应性强、处理能力大、金属回收率高、易于机械操作、劳动强度低的优点，自原锡矿山矿务局研究成功后，在我国获得快速发展，现已成为我国主要的锑冶炼方法。但“低料柱、薄料层、高焦率、高温炉顶”的特殊作业条件决定了该工艺存在焦率大、能耗高、炉寿短、烟气冷却和收尘系统庞杂的弊端，尤其是排放出大量的低浓度SO 2烟气严重污染生态环境，至今没有一个经济、高效的技术解决方案。随着国家“三废”排放标准的不断提高，能否实现低碳、清洁环保炼锑现已成为关乎我国锑冶炼企业可持续发展的关键问题。 Antimony is a rare strategic metal widely used in flame retardant, alloys, ceramics, pigments, semiconductors and chemical industries. The raw material for antimony smelting in China is mainly antimony ore (Sb 2 S 3 ). At present, antimony smelting enterprises mainly use the "blast furnace volatilization-reverberatory furnace reduction smelting" process to produce metallic antimony. That is, after the antimony is granulated, it is added to the blast furnace together with coke and flux for volatilization and smelting, so that the antimony enters the high-temperature flue gas and is recovered in the form of crude antimony oxide after condensation and dust collection. The low-concentration SO 2 generated during the smelting process is desulfurized and discharged null. Then, the crude antimony oxide is reduced and smelted in a reverberatory furnace to obtain crude antimony metal. Blast furnace volatilization smelting has the advantages of strong raw material adaptability, large processing capacity, high metal recovery rate, easy mechanical operation, and low labor intensity. Since the successful research of the Yuan Tin Mine Bureau, it has developed rapidly in our country and has now become a major Antimony smelting method. However, the special operating conditions of "low material column, thin material layer, high coke rate, and high temperature furnace top" determine that this process has the disadvantages of high coke rate, high energy consumption, short furnace life, and complicated flue gas cooling and dust collection systems. In particular, a large amount of low-concentration SO 2 flue gas is emitted, which seriously pollutes the ecological environment. So far, there is no economical and efficient technical solution. With the continuous improvement of national "three wastes" emission standards, whether low-carbon, clean and environmentally friendly antimony smelting can be achieved has now become a key issue related to the sustainable development of my country's antimony smelting enterprises.
火法冶炼新技术研究的焦点主要集中在将富氧顶吹、底吹、侧吹等强化熔池熔炼技术引入锑冶炼，该尝试主要是提高SO 2烟气浓度来制酸，避免低浓度SO 2的排放。但由于Sb 2S 3高温易挥发分解，且易与FeS形成锑锍等特点，使得Sb 2S 3富氧熔池熔炼时极易出现“结瘤”堵塞炉膛、烟道及“死炉”等问题，导致富氧熔池熔炼技术难以适用于锑冶炼。因此，想要解决锑冶炼工艺存在的焦炭使用量大，低浓度SO 2污染的问题，一个技术和经济上更为合理的低碳、清洁、高效一步炼锑的方法有待推出。 The focus of research on new technologies for pyrometallurgy is mainly focused on introducing enhanced molten pool smelting technologies such as oxygen-rich top blowing, bottom blowing, and side blowing into antimony smelting. This attempt is mainly to increase the concentration of SO 2 flue gas to produce acid and avoid low-concentration SO 2 emissions. However, due to the characteristics of Sb 2 S 3 , which is easy to volatilize and decompose at high temperatures, and easily forms antimony and matte with FeS, it is easy for "nodules" to block the furnace, flue and "dead furnace" during Sb 2 S 3 oxygen-rich molten pool melting. Problems make it difficult for oxygen-rich molten pool smelting technology to be applied to antimony smelting. Therefore, in order to solve the problems of large coke usage and low-concentration SO2 pollution in the antimony smelting process, a more technically and economically reasonable low-carbon, clean, and efficient one-step antimony smelting method needs to be launched.
技术问题technical problem
近年来，辉锑矿的低温熔盐电解炼锑技术发展迅速，发明人曾发明“一种锑锑的低温熔盐电解清洁冶金方法及装置（中国专利 201710775124.0）”以及“一种含硫化锑物料熔盐电解的方法及装置（中国专利 202010114724.4）”，但在后续规模化放大连续生产的应用实践中却发现几项重大的不足：一是辉锑矿熔盐电解后，熔盐残渣中的硫化锑含量仍较高，直接排放将导致大量锑的损失，而若在一个电解炉内一直进行恒流或恒压电解，则随着时间延长，炉内熔盐电阻上升，电极表面发生副反应程度加重；二是单个电解炉不利于整个电解工艺的连续化生产，净化熔盐和排渣过程中将导致电解炉的停用，不利于工业生产效率的提高；三是电解过程中熔盐中实际物料浓度对工艺参数的调控要求不一样，实际操作中单个电解炉难以实现针对所需最佳工艺参数的实时调控，导致最终得到的粗锑电流效率和电解能耗不理想。因此，有必要提供一种经济和技术上可行的方法，实现锑矿熔盐电解连续化工业生产锑的工艺及装置。In recent years, the low-temperature molten salt electrolysis antimony refining technology of stibnite has developed rapidly. The inventor has invented “a low-temperature molten salt electrolysis cleaning metallurgical method and device for antimony (Chinese patent 201710775124.0)” and “an antimony sulfide-containing material. Methods and devices for molten salt electrolysis (Chinese patent 202010114724.4)", but in the subsequent application practice of large-scale amplification of continuous production, several major deficiencies were discovered: First, after the electrolysis of antimony molten salt, the sulfide in the molten salt residue The antimony content is still high, and direct emission will result in the loss of a large amount of antimony. If constant current or constant voltage electrolysis is carried out in an electrolytic furnace, as time goes by, the resistance of the molten salt in the furnace will increase, and side reactions will occur on the electrode surface. Secondly, a single electrolytic furnace is not conducive to the continuous production of the entire electrolysis process. The process of purifying molten salt and slag removal will lead to the outage of the electrolytic furnace, which is not conducive to the improvement of industrial production efficiency; thirdly, the actual amount of molten salt in the electrolysis process is The material concentration has different requirements for the control of process parameters. In actual operation, it is difficult for a single electrolysis furnace to achieve real-time control of the required optimal process parameters, resulting in unsatisfactory current efficiency and electrolysis energy consumption of the final crude antimony. Therefore, it is necessary to provide an economically and technically feasible method to realize a process and device for the continuous industrial production of antimony through molten salt electrolysis of antimony ore.
技术解决方案Technical solutions
针对上述问题，本发明的目的在于提供一种含硫化锑矿熔盐电解连续化生产的方法，采用两个电解炉分段炼锑，以解决目前单一的电解炉，即专利201710775124.0和202010114724.4中所述的含硫化锑矿熔盐电解炼锑方法无法实现真正意义上的连续生产，电流效率较低、电解能耗高，电解过程参数难以实时调控，残渣中锑含量较高的问题。In response to the above problems, the purpose of the present invention is to provide a method for the continuous electrolysis production of molten salts containing antimony sulfide ores, using two electrolytic furnaces to smelt antimony in sections, so as to solve the problem of the current single electrolytic furnace, namely patents 201710775124.0 and 202010114724.4. The above-mentioned antimony sulfide-containing ore molten salt electrolysis antimony refining method cannot achieve continuous production in the true sense. The current efficiency is low, the electrolysis energy consumption is high, the electrolysis process parameters are difficult to control in real time, and the antimony content in the residue is high.
本发明的目的是通过以下技术方案实现：The purpose of the present invention is achieved through the following technical solutions:
一种硫化锑矿熔盐电解连续化生产的方法，包括以下步骤：A method for continuous electrolysis production of antimony sulfide ore molten salt, including the following steps:
（1）将硫化锑矿和共晶熔盐置于高锑电解炉内进行恒电流限压升温电解熔炼，熔炼过程中吹入惰性气体搅动熔体，金属锑液和单质硫分别从高锑电解炉的放锑口、高锑电解炉的烟气口排出；(1) Place antimony sulfide ore and eutectic molten salt in a high antimony electrolytic furnace for constant current, limited voltage and temperature rise electrolytic smelting. During the smelting process, inert gas is blown into the melt to stir the melt, and the metallic antimony liquid and elemental sulfur are electrolyzed from high antimony respectively. The antimony discharge port of the furnace and the smoke port of the high antimony electrolytic furnace are discharged;
（2）将步骤（1）得到的电解后熔体通过溜槽进入贫化电解炉内进行恒电压贫化电解，电解前补充熔盐，金属锑液和单质硫分别从贫化电解炉的放锑口、贫化电解炉的烟气口排出，贫化后渣由排渣口放出。(2) Enter the electrolyzed melt obtained in step (1) through the chute into the depletion electrolytic furnace for constant voltage depletion electrolysis. Before electrolysis, replenish molten salt, metallic antimony liquid and elemental sulfur to discharge antimony from the depletion electrolytic furnace respectively. The flue gas port of the depleted electrolytic furnace is discharged, and the depleted slag is released from the slag discharge port.
所述的方法，步骤（1）中，硫化锑矿与共晶熔盐的质量百分比为10:1～5:4，，优选为6:1～5:2。In the described method, in step (1), the mass percentage of antimony sulfide ore and eutectic molten salt is 10:1 to 5:4, preferably 6:1 to 5:2.
进一步地，所述共晶熔盐为氯化钠和氯化钾的混合物，氯化钠与氯化钾的质量百分比为7:3～2:7，优选为4:5～2:5。Further, the eutectic molten salt is a mixture of sodium chloride and potassium chloride, and the mass percentage of sodium chloride and potassium chloride is 7:3-2:7, preferably 4:5-2:5.
所述的方法，步骤（1）中，高锑电解炉内温度为700～950℃，升温速率为8～15℃/min，优选为850～900℃。In the described method, in step (1), the temperature in the high antimony electrolysis furnace is 700-950°C, and the heating rate is 8-15°C/min, preferably 850-900°C.
所述的方法，步骤（1）中，电解熔炼时阳极电流密度为1000～5000 A·m -2，优选为2000～3000 A·m -2；槽电压控制在4 V以下，优选控制在3.8 V以下；阴阳极间距为1～8cm，优选为2～4cm。 In the described method, in step (1), the anode current density during electrolytic smelting is 1000-5000 A·m -2 , preferably 2000-3000 A·m -2 ; the cell voltage is controlled below 4 V, preferably 3.8 V or less; the distance between anode and cathode is 1 to 8cm, preferably 2 to 4cm.
所述的方法，步骤（1）中，惰性气体优选为氮气或氩气，吹入惰性气体的压力为0.12～0.35MPa，惰性气体流量为40～1100 L/(min·m 3)。 In the described method, in step (1), the inert gas is preferably nitrogen or argon, the pressure of the inert gas blown is 0.12-0.35MPa, and the inert gas flow rate is 40-1100 L/(min·m 3 ).
进一步地，惰性气体吹入前需预热，优选预热气体温度为700～950℃。Furthermore, the inert gas needs to be preheated before blowing in. The preferred temperature of the preheated gas is 700 to 950°C.
对惰性气体进行预热，可防止高锑电解炉内局部温度过冷导致熔体温度不够，影响电解效率。Preheating the inert gas can prevent the local temperature in the high antimony electrolysis furnace from being too cold, resulting in insufficient melt temperature and affecting the electrolysis efficiency.
所述的方法，步骤（1）中，电解熔炼反应时间为2～20h，优选为8～15h。In the described method, in step (1), the electrolytic smelting reaction time is 2 to 20 hours, preferably 8 to 15 hours.
在本发明中，高锑电解炉，采用恒电流限电压和惰性气体吹入搅动熔盐的电解方式，且根据理论消耗量补充物料，包括电解消耗和挥发损失，补充物料为硫化锑矿、氯化钠及氯化钾的混合物。In the present invention, the high antimony electrolysis furnace adopts the electrolysis method of constant current limiting voltage and inert gas blowing to stir the molten salt, and replenishing materials according to the theoretical consumption, including electrolysis consumption and volatilization loss. The replenishing materials are antimony sulfide ore, chlorine A mixture of sodium chloride and potassium chloride.
通过补充硫化锑矿、氯化钠及氯化钾的混合物，可以保持电解炉内物料浓度充足、均匀且稳定。By supplementing the mixture of antimony sulfide ore, sodium chloride and potassium chloride, the material concentration in the electrolysis furnace can be maintained sufficient, uniform and stable.
所述的方法，步骤（2）中，贫化电解前补充的熔盐为共晶熔盐，熔盐补充量为5～40%（以高锑电解炉出来的熔体为基准的5～40%）。In the described method, in step (2), the molten salt supplemented before the depletion electrolysis is eutectic molten salt, and the molten salt supplementary amount is 5 to 40% (5 to 40% based on the melt coming out of the high antimony electrolysis furnace). %).
电解前补充熔盐可以降低高锑电解炉出来熔体的粘度值，降低电解过程的能耗损失以及便于后续贫化渣的排放，基于不同熔盐补充量的试验所得电流效率、能耗的结果确定熔盐的补充量。Supplementing molten salt before electrolysis can reduce the viscosity value of the melt coming out of the high antimony electrolysis furnace, reduce the energy consumption loss in the electrolysis process and facilitate the subsequent discharge of depleted slag. Results of current efficiency and energy consumption based on experiments with different amounts of molten salt supplementation. Determine the amount of molten salt to replenish.
所述的方法，步骤（2）中，贫化电解炉内温度为700～1050℃，升温速率为8～15℃/min，优选为850～950℃。In the described method, in step (2), the temperature in the depletion electrolysis furnace is 700-1050°C, and the heating rate is 8-15°C/min, preferably 850-950°C.
贫化电解炉内温度要高于高锑电解炉内温度，由于温度越高熔体的粘度越小，提高温度和补充熔盐都是为了降低贫化电解槽内的熔体粘度值，以便提高电解过程的电流效率和降低电解能耗。The temperature in the depleted electrolytic furnace is higher than the temperature in the high antimony electrolytic furnace. Since the higher the temperature, the smaller the viscosity of the melt. Increasing the temperature and supplementing molten salt are both to reduce the viscosity of the melt in the depleted electrolytic bath, so as to improve The current efficiency of the electrolysis process and the reduction of electrolysis energy consumption.
所述的方法，步骤（2）中，贫化电解时槽电压为1.5～4.5 V，优选为2.5～3.5 V；阴阳极间距为1～8cm，优选为2～4cm。In the described method, in step (2), the cell voltage during depletion electrolysis is 1.5-4.5 V, preferably 2.5-3.5 V; the distance between cathodes and anodes is 1-8 cm, preferably 2-4 cm.
所述的方法，步骤（2）中，贫化电解反应时间为2～6h，优选为3～4h；贫化电解后排渣口放出的渣中锑＜1wt.%。In the described method, in step (2), the depletion electrolysis reaction time is 2 to 6 hours, preferably 3 to 4 hours; the antimony in the slag discharged from the slag outlet after the depletion electrolysis is <1wt.%.
在本发明中，贫化电解炉，以恒电压电解方式贫化电解高锑电解炉的电解后熔体，使得最终残渣中锑达到较低水平（贫化电解后排渣口放出的渣中锑＜1wt.%），并使熔盐与矿物中的脉石等组分分离，实现杂质的开路。In the present invention, the depleted electrolytic furnace uses constant voltage electrolysis to deplete the post-electrolysis melt of the electrolytic high antimony electrolysis furnace, so that the antimony in the final residue reaches a lower level (the antimony in the slag released from the slag outlet after depletion electrolysis <1wt.%), and separate the molten salt from the gangue and other components in the mineral to achieve the opening of impurities.
本发明中，首次将两连炉结合到硫化锑矿的熔盐电解炼锑的过程，通过对高锑电解炉电解后锑液由放锑口排出，剩余的含脉石等杂质和未电解完的硫化锑熔体通过溜槽一并进入贫化电解炉，补充一定熔盐后进行恒电压贫化电解，以使得最终排放的残渣中锑在一个较低的水平。In the present invention, for the first time, two consecutive furnaces are combined into the process of antimony refining by molten salt electrolysis of antimony sulfide ores. After electrolysis in the high-antimony electrolytic furnace, the antimony liquid is discharged from the antimony discharge port. The remaining impurities including gangue and unelectrolyzed The antimony sulfide melt enters the depletion electrolytic furnace through the chute. After adding a certain amount of molten salt, constant voltage depletion electrolysis is performed, so that the antimony in the final discharged residue is at a lower level.
本发明创造性地对高锑电解炉进行恒电流限压电解，而对贫化电解炉则是进行恒电压贫化电解，通过这样的方式组合，可以有效降低残渣中锑含量和节省能耗。原因如下：由于高锑电解炉内锑浓度较高，恒电流限电压电解锑的过程电流效率高、电解能耗低，但若一直保持恒电流限电压电解，杂质的积累将导致熔体物性变化，电流效率降低，能耗增大，因此需转移至贫化电解炉。由于贫化电解炉随着电解的进行，锑的浓度越来越低，若继续采用恒电流电解，熔盐中硫化锑浓度无法满足电极附近电化学反应需求，将不可避免的导致副反应增加，造成电解能耗的急剧增加。所以对贫化电解炉采用恒电压电解，使得实际电流密度随着熔体物性变化而变化，实现降低残渣中锑含量和节省能耗的目的。The invention creatively performs constant current and voltage limiting electrolysis in the high antimony electrolytic furnace, and performs constant voltage depletion electrolysis in the depleted electrolytic furnace. Through this combination, the antimony content in the residue can be effectively reduced and energy consumption can be saved. The reasons are as follows: Due to the high concentration of antimony in the high-antimony electrolysis furnace, the process of constant current and voltage-limited electrolysis of antimony has high current efficiency and low electrolysis energy consumption. However, if constant current and voltage-limited electrolysis is maintained, the accumulation of impurities will lead to changes in the physical properties of the melt. , the current efficiency decreases and energy consumption increases, so it needs to be transferred to a depleted electrolysis furnace. Since the concentration of antimony in the depleted electrolysis furnace becomes lower and lower as the electrolysis proceeds, if galvanostatic electrolysis continues to be used, the concentration of antimony sulfide in the molten salt cannot meet the needs of the electrochemical reaction near the electrode, which will inevitably lead to an increase in side reactions. Causes a sharp increase in electrolysis energy consumption. Therefore, constant voltage electrolysis is used in the depletion electrolysis furnace, so that the actual current density changes with the changes in the physical properties of the melt, thereby achieving the purpose of reducing the antimony content in the residue and saving energy consumption.
根据贫化电解炉所需熔体的物性特征，对熔盐补充量、槽电压、极间距及电解温度分别控制在上述范围内，电解效率最高，能耗最低，这是由于熔盐的补充、温度的升高，能有效改善熔盐的粘度、电导率等物性，更利于熔盐电解的进行。同时，恒电压过程能有效保证在电解过程根据熔体中硫化锑浓度来调控电流密度的大小，避免电能的过度空耗。According to the physical properties of the melt required for the depleted electrolysis furnace, the molten salt supplement, cell voltage, electrode spacing and electrolysis temperature are controlled within the above ranges respectively. The electrolysis efficiency is the highest and the energy consumption is the lowest. This is due to the molten salt supplement, The increase in temperature can effectively improve the viscosity, conductivity and other physical properties of the molten salt, which is more conducive to the progress of molten salt electrolysis. At the same time, the constant voltage process can effectively ensure that the current density is controlled according to the concentration of antimony sulfide in the melt during the electrolysis process to avoid excessive waste of electrical energy.
本发明的另一个目的在于提供一种与上述含硫化锑矿熔盐电解连续化生产的方法配套的一种组合熔盐电解炉装置。Another object of the present invention is to provide a combined molten salt electrolysis furnace device matched with the above-mentioned method for continuous electrolysis production of molten salt containing antimony sulfide ores.
包括结构相同的两个电解炉，所述的电解炉包括中空的炉体和设置于炉体内的电解单元；所述的炉体在上部分别设有入料口和烟气口，在下部分别设有放锑口和排渣口；其中一个电解炉作为高锑电解炉，且排渣口的位置高于另一个作为贫化电解炉的入料口，高锑电解炉的排渣口通过溜槽连接至贫化电解炉的入料口；高锑电解炉设有伸入至炉体内吹入惰性气体的气体喷枪。It includes two electrolytic furnaces with the same structure. The electrolytic furnace includes a hollow furnace body and an electrolysis unit arranged in the furnace body; the furnace body is provided with a feed inlet and a flue gas port respectively in the upper part, and is respectively provided in the lower part. There is an antimony discharge port and a slag discharge port; one of the electrolytic furnaces is used as a high antimony electrolytic furnace, and the slag discharge port is located higher than the feed port of the other as a depleted electrolytic furnace. The slag discharge port of the high antimony electrolytic furnace is connected through a chute. To the feed inlet of the depletion electrolytic furnace; the high antimony electrolytic furnace is equipped with a gas lance that extends into the furnace body and blows inert gas.
进一步地，电解炉的外壁上设有热电阻，且热电阻外包覆有保温层；所述溜槽设有放料阀门和取样观测口，溜槽内熔体的流动速度为0.1～0.8 m·s -1； Further, a thermal resistor is provided on the outer wall of the electrolysis furnace, and the thermal resistor is covered with an insulation layer; the chute is equipped with a discharge valve and a sampling observation port, and the flow rate of the melt in the chute is 0.1 to 0.8 m·s. -1 ;
所述的电解单元包括设置于炉体内底部的阴极和设置于炉体上部的阳极，所述的阳极连接伸出至炉体外的阳极导杆，以通过导线连接电源正极；所述的阴极通过导线连接电源负极。The electrolysis unit includes a cathode arranged at the bottom of the furnace body and an anode arranged at the upper part of the furnace body. The anode is connected to an anode guide rod extending out of the furnace body to connect the positive electrode of the power supply through a wire; the cathode is connected through a wire Connect the negative terminal of the power supply.
所述气体喷枪、阳极导杆的材质为氧化铝。The gas spray gun and anode guide rod are made of aluminum oxide.
由给料器连续补料和气体喷枪搅动熔体，电解所得锑液由放锑口排出，含硫烟气从烟气口被收集，炉渣由排渣口排出。The feeder continuously feeds the material and the gas spray gun stirs the melt. The antimony liquid obtained by electrolysis is discharged from the antimony discharge port. The sulfur-containing flue gas is collected from the flue gas port, and the slag is discharged from the slag discharge port.
从溜槽的取样观测口进行取样分析，以实现贫化电解炉电解工艺参数的优化调控。通过溜槽的放料阀门、取样观测口可将贫化电解炉所得电解物料的量进行调控以及组分物性的观测，将溜槽的熔体流动控制在上述优选范围内，可有效避免熔体热量的损失或溜槽的堵塞。Sampling and analysis are carried out from the sampling observation port of the chute to achieve optimal control of the electrolysis process parameters of the depletion electrolysis furnace. Through the discharge valve and sampling observation port of the chute, the amount of electrolytic materials obtained from the depleted electrolysis furnace can be controlled and the physical properties of the components can be observed. The melt flow in the chute can be controlled within the above preferred range, which can effectively avoid the loss of melt heat. loss or blockage of the chute.
有益效果beneficial effects
综上所述，与现有技术（专利201710775124.0和202010114724.4）相比较，本发明的一种含硫化锑矿熔盐电解连续化生产的方法及装置具有以下优势：In summary, compared with the existing technology (Patents 201710775124.0 and 202010114724.4), the method and device for the continuous electrolysis production of antimony sulfide ore molten salt of the present invention have the following advantages:
（1）高锑电解炉和贫化电解炉的两连炉熔盐电解炼锑的设计，使得整个电解过程能够根据需求在两种不同的工艺参数下同时进行，满足硫化锑物料熔盐电解过程中，惰性气体鼓吹搅动的恒电流电解，实现高电流效率，以及静态贫化恒电压电解过程，实现熔盐电解渣含锑低，熔盐与渣组分分层、分离的目的；完全满足工业生产过程的技术经济可行的需求。(1) The design of the two-furnace molten salt electrolysis antimony smelting of high antimony electrolytic furnace and depleted electrolytic furnace enables the entire electrolysis process to be carried out simultaneously under two different process parameters according to needs, meeting the needs of the molten salt electrolysis process of antimony sulfide materials. In the process, the inert gas blows and stirs the constant current electrolysis to achieve high current efficiency, and the static depletion constant voltage electrolysis process realizes the purpose of low antimony content in the molten salt electrolytic slag and the stratification and separation of the molten salt and slag components; fully satisfying the industrial needs Technologically and economically viable requirements for the production process.
（2）本发明设计的高锑电解炉和贫化电解炉存在一个高度差，并且两电解炉由溜槽连接为一个整体，完全实现含硫化锑矿的熔盐电解连续化生产。(2) There is a height difference between the high antimony electrolytic furnace and the depleted electrolytic furnace designed in the present invention, and the two electrolytic furnaces are connected as a whole by a chute, fully realizing the continuous production of molten salt electrolysis of antimony sulfide-containing ores.
（3）本发明经贫化电解炉对于高锑电解炉的电解后熔体的贫化电解和脉石等组分的分离净化，实现惰性熔盐的循环与回用，大大降低了硫化锑矿熔盐电解的原料成本。(3) The present invention realizes the circulation and reuse of inert molten salt through the depletion electrolysis of the melt after electrolysis in the high antimony electrolysis furnace and the separation and purification of components such as gangue, which greatly reduces the cost of antimony sulfide ores. Raw material costs for molten salt electrolysis.
（4）本发明与现行锑冶炼“鼓风炉氧化挥发—反射炉还原”的冶炼工艺相比，本发明可实现完整的连续化生产一步炼锑，且大幅降低锑精矿火法冶炼温度，直接产出金属锑和单质硫，无SO 2排放，具有能耗低，锑、硫直收率高的优点，对促进我国锑冶金技术进步和节能减排具有重大意义。 (4) Compared with the current smelting process of "blast furnace oxidation and volatilization - reverberatory furnace reduction" for antimony smelting, the present invention can achieve complete continuous production of one-step antimony smelting, and significantly reduce the pyrometallurgical smelting temperature of antimony concentrate, directly producing It produces metallic antimony and elemental sulfur without SO2 emissions. It has the advantages of low energy consumption and high direct recovery rate of antimony and sulfur. It is of great significance to promote the progress of China's antimony metallurgical technology and energy conservation and emission reduction.
附图说明Description of the drawings
图1为本发明的含硫化锑矿熔盐电解连续化生产装置示意图（1-给料器，2-热电阻，3-放锑口，4-气体喷枪，5-阳极导杆，6-高锑电解炉，7-烟气口，8-石墨阳极，9-溜槽，10-石墨阴极，11-取样观测口，12-粗锑槽，13-贫化电解炉，14-保温层，15-排渣口，16-直流电源，17-炉渣，18-硫化锑，19-熔盐，20-锑液）。Figure 1 is a schematic diagram of the continuous electrolysis production device of molten salt containing antimony sulfide ore according to the present invention (1-feeder, 2-thermal resistor, 3-antimony discharge port, 4-gas spray gun, 5-anode guide rod, 6-height Antimony electrolytic furnace, 7-flue gas port, 8-graphite anode, 9-chute, 10-graphite cathode, 11-sampling observation port, 12-coarse antimony tank, 13-depletion electrolytic furnace, 14-insulation layer, 15- Slag discharge port, 16-DC power supply, 17-slag, 18-antimony sulfide, 19-molten salt, 20-antimony liquid).
本发明的实施方式Embodiments of the invention
以下实施例旨在进一步说明本发明，而不会形成对本发明的限定。The following examples are intended to further illustrate the present invention without limiting it.
本实施例中的两连炉熔盐电解装置，是采用了结构相同的两个电解炉，其中每个电解炉都包括中空的炉体和设置于炉体内的电解单元。而炉体在上部分别设有入料口和烟气口，在下部分别设有放锑口和排渣口。同时炉体的外壁上设有热电阻，且热电阻外包覆有保温层，通过热电阻来对熔体进行升温加热。然后将其中一个电解炉作为高锑电解炉，且这个高锑电解炉的排渣口的位置高于另一个作为贫化电解炉的入料口，再通过溜槽将高锑电解炉的排渣口和贫化电解炉的入料口连接起来，溜槽上设有放料阀门以启动或停止放料，同时还设有取样观测口，以便于从溜槽取样，溜槽内熔体的流动速度为0.1～0.8 m·s -1。高锑电解炉还设有伸入至炉体内吹入惰性气体的气体喷枪，以吹入惰性气体来搅动熔盐。电解所得锑液由放锑口排出，含硫烟气从烟气口被收集。贫化电解炉的炉渣由排渣口排出。 The two-furnace molten salt electrolysis device in this embodiment uses two electrolytic furnaces with the same structure, in which each electrolytic furnace includes a hollow furnace body and an electrolysis unit arranged in the furnace body. The furnace body is equipped with a feeding port and a flue gas port on the upper part, and an antimony discharging port and a slag discharging port on the lower part. At the same time, a thermal resistor is provided on the outer wall of the furnace body, and the thermal resistor is covered with an insulation layer. The melt is heated by the thermal resistor. Then one of the electrolytic furnaces is used as a high antimony electrolytic furnace, and the slag discharge port of this high antimony electrolytic furnace is positioned higher than the feed port of the other as a depleted electrolytic furnace. The slag discharge port of the high antimony electrolytic furnace is then moved through the chute. Connected to the feed inlet of the depletion electrolysis furnace, the chute is equipped with a discharge valve to start or stop the discharge. It is also equipped with a sampling observation port to facilitate sampling from the chute. The flow rate of the melt in the chute is 0.1~ 0.8 m·s -1 . The high antimony electrolysis furnace is also equipped with a gas lance that extends into the furnace body and blows inert gas to stir the molten salt. The antimony liquid obtained by electrolysis is discharged from the antimony discharge port, and the sulfur-containing flue gas is collected from the flue gas port. The slag of the depleted electrolytic furnace is discharged from the slag discharge port.
炉体中的电解单元包括设置于炉体内底部的阴极和设置于炉体上部的阳极，其中阳极连接伸出至炉体外的阳极导杆，以通过导线连接电源正极，阴极则通过导线直接连接电源负极。The electrolysis unit in the furnace body includes a cathode located at the bottom of the furnace body and an anode located at the upper part of the furnace body. The anode is connected to an anode guide rod extending out of the furnace body to connect the positive electrode of the power supply through a wire, and the cathode is directly connected to the power supply through a wire. negative electrode.
以下实施例均采用上述装置。The following examples all adopt the above device.
实施例1Example 1
硫化锑精矿A的化学组成为（wt. %）：Sb 52.91、S 23.12、Si 7.15、Fe 1.61、As 0.53、Al 1.08、Pb 0.29、Ca 0.33、Mg 0.14。称取硫化锑与熔盐质量百分比为5:1的混合物料，依次置于高锑电解炉中，开启热电阻升高温度至900℃，调整电极间距为4cm，开启气体喷枪控制气体压力为0.15MPa，流量为185 L/(min·m 3)。启动电源设置电流密度大小为2100 A·m -2，限槽电压为3.8V，按照理论消耗量持续补料，电解9h后，放出粗锑，收集含硫烟尘，其余的高锑电解炉熔体经过溜槽进入贫化电解炉，并补充熔盐20%（以高锑电解炉出来的熔体为基准计算），电解炉内温度控制在950℃，接通电源槽电压控制为3 V，电解3h后停止电解，静止分层后，依次从放锑口、排渣口放出粗锑、熔盐与炉渣，从烟气口收集含硫烟尘。电解炉的全流程电流效率为90.8%，电解能耗为2.35kWh·kg -1，电解残渣中含锑0.56%。 The chemical composition of antimony sulfide concentrate A is (wt. %): Sb 52.91, S 23.12, Si 7.15, Fe 1.61, As 0.53, Al 1.08, Pb 0.29, Ca 0.33, Mg 0.14. Weigh a mixture of antimony sulfide and molten salt with a mass percentage of 5:1, place it in a high antimony electrolytic furnace, turn on the thermal resistor to increase the temperature to 900°C, adjust the electrode spacing to 4cm, and turn on the gas spray gun to control the gas pressure to 0.15 MPa, the flow rate is 185 L/(min·m 3 ). Start the power supply and set the current density to 2100 A·m -2 and the cell voltage limit to 3.8V. Continue to replenish materials according to the theoretical consumption. After 9 hours of electrolysis, release the crude antimony, collect sulfur-containing smoke and dust, and the remaining high antimony electrolytic furnace melt Enter the depleted electrolytic furnace through the chute, and add 20% of molten salt (calculated based on the melt coming out of the high antimony electrolytic furnace). The temperature in the electrolytic furnace is controlled at 950°C. The voltage of the power tank is turned on and controlled at 3 V. Electrolysis lasts for 3 hours. Finally, the electrolysis is stopped. After static stratification, crude antimony, molten salt and slag are discharged from the antimony discharge port and slag discharge port in sequence, and sulfur-containing smoke and dust are collected from the flue gas port. The entire process current efficiency of the electrolysis furnace is 90.8%, the electrolysis energy consumption is 2.35kWh·kg -1 , and the electrolysis residue contains 0.56% antimony.
实施例2Example 2
硫化锑精矿B的化学组成为（wt. %）：Sb 32.56、S 28.12、Si 2.51、Fe 5.61、As 2.53、Al 1.12、Pb 0.45、Ca 0.31、Mg 0.28。称取硫化锑与熔盐质量百分比为5:1的混合物料，依次置于高锑电解炉中，开启热电阻升高温度至900℃，调整电极间距为4cm，开启气体喷枪控制气体压力为0.15MPa，流量为185 L/(min·m 3)。启动电源设置电流密度大小为2100 A·m -2，限槽电压为3.8V，按照理论消耗量持续补料，电解9h后，放出粗锑，收集含硫烟尘，其余的高锑电解炉熔体经过溜槽进入贫化电解炉，并补充熔盐20%（以高锑电解炉出来的熔体为基准计算），电解炉内温度控制在950℃，接通电源槽电压控制为3 V，电解3h后停止电解，静止分层后，依次从放锑口、排渣口放出粗锑、熔盐与炉渣，从烟气口收集含硫烟尘。电解炉的全流程电流效率为86.7%，电解能耗为2.64kWh·kg -1，电解残渣中含锑0.82%。 The chemical composition of antimony sulfide concentrate B is (wt. %): Sb 32.56, S 28.12, Si 2.51, Fe 5.61, As 2.53, Al 1.12, Pb 0.45, Ca 0.31, Mg 0.28. Weigh a mixture of antimony sulfide and molten salt with a mass percentage of 5:1, place it in a high antimony electrolytic furnace, turn on the thermal resistor to increase the temperature to 900°C, adjust the electrode spacing to 4cm, and turn on the gas spray gun to control the gas pressure to 0.15 MPa, the flow rate is 185 L/(min·m 3 ). Start the power supply and set the current density to 2100 A·m -2 and the cell voltage limit to 3.8V. Continue to replenish materials according to the theoretical consumption. After 9 hours of electrolysis, release the crude antimony, collect sulfur-containing smoke and dust, and the remaining high antimony electrolytic furnace melt Enter the depleted electrolytic furnace through the chute, and add 20% of molten salt (calculated based on the melt coming out of the high antimony electrolytic furnace). The temperature in the electrolytic furnace is controlled at 950°C. The voltage of the power tank is turned on and controlled at 3 V. Electrolysis lasts for 3 hours. Finally, the electrolysis is stopped. After static stratification, crude antimony, molten salt and slag are discharged from the antimony discharge port and slag discharge port in sequence, and sulfur-containing smoke and dust are collected from the flue gas port. The full-process current efficiency of the electrolysis furnace is 86.7%, the electrolysis energy consumption is 2.64kWh·kg -1 , and the electrolysis residue contains 0.82% antimony.
实施例3Example 3
同上述实施例1相同原料。称取硫化锑与熔盐比例为6:1的混合物料，依次置于高锑电解炉中，开启热电阻升高温度至850℃，调整电极间距为5cm，开启气体喷枪控制气体压力为0.15MPa，流量为185 L/(min·m 3)。启动电源设置电流密度大小为1800 A·m -2，槽电压为4.0V，按照理论消耗量持续补料，电解15h后，放出粗锑，收集含硫烟尘，其余的高锑电解炉熔体经过溜槽进入贫化电解炉，并补充熔盐10%（以高锑电解炉出来的熔体为基准计算），电解炉内温度控制在900℃，接通电源槽电压控制为2 V，电解5h后停止电解，静止分层后，依次从放锑口、排渣口放出粗锑、熔盐与炉渣，从烟气口收集含硫烟尘。电解炉全流程电流效率为85.8%，电解能耗为2.83kWh·kg -1，电解残渣中含锑0.95%。 The same raw materials as in Example 1 above. Weigh the mixture of antimony sulfide and molten salt with a ratio of 6:1, place it in a high antimony electrolytic furnace, turn on the thermal resistor to increase the temperature to 850°C, adjust the electrode spacing to 5cm, and turn on the gas spray gun to control the gas pressure to 0.15MPa , the flow rate is 185 L/(min·m 3 ). Start the power supply and set the current density to 1800 A·m -2 and the cell voltage to 4.0V. Continue to add materials according to the theoretical consumption. After 15 hours of electrolysis, the crude antimony is released and the sulfur-containing smoke is collected. The remaining high antimony electrolytic furnace melt passes through The chute enters the depleted electrolytic furnace, and 10% of the molten salt is added (calculated based on the melt coming out of the high antimony electrolytic furnace). The temperature in the electrolytic furnace is controlled at 900°C, and the voltage of the tank is controlled at 2 V when the power is turned on. After electrolysis for 5 hours Stop electrolysis, and after static stratification, release crude antimony, molten salt and slag from the antimony discharge port and slag discharge port in sequence, and collect sulfur-containing smoke and dust from the flue gas port. The current efficiency of the entire electrolysis furnace process is 85.8%, the electrolysis energy consumption is 2.83kWh·kg -1 , and the electrolysis residue contains 0.95% antimony.
对比例1Comparative example 1
此对比例为单一电解炉气体搅动恒电压熔盐电解方案：同上述实施例1相同原料，按照专利“一种含硫化锑物料熔盐电解的方法及装置（中国专利 202010114724.4）”中所述的方案开展熔盐电解试验，不同之处是电解周期延长为12h，电解过程补料量与实施例1相同。试验结束后，根据所得粗锑计算，电流效率为72.85%，电解能耗为3.65kWh·kg -1，炉渣与熔盐的分层效果差，且渣中锑含量为2.56%。 This comparative example is a single electrolytic furnace gas agitation constant voltage molten salt electrolysis scheme: the same raw materials as the above-mentioned Example 1, according to the patent "A method and device for molten salt electrolysis of antimony sulfide-containing materials (Chinese Patent 202010114724.4)" The plan is to carry out a molten salt electrolysis test. The difference is that the electrolysis cycle is extended to 12 hours, and the amount of feed during the electrolysis process is the same as in Example 1. After the test, calculated based on the crude antimony obtained, the current efficiency was 72.85%, the electrolysis energy consumption was 3.65kWh·kg -1 , the stratification effect of the slag and molten salt was poor, and the antimony content in the slag was 2.56%.
对比例2Comparative example 2
此对比例为单一电解炉无气体搅动恒电压熔盐电解方案：同上述实施例1相同原料，按照专利“一种的低温熔盐电解清洁冶金方法及装置（中国专利 201710775124.0）”中所述的方案开展熔盐电解试验，不同之处是电解周期延长为12h，电解过程补料量与实施例1相同。试验结束后，根据所得粗锑计算，电流效率为65.23%，电解能耗为3.86kWh·kg -1，渣中锑含量为1.58%。 This comparative example is a single electrolytic furnace non-gas agitation constant voltage molten salt electrolysis scheme: the same raw materials as the above-mentioned Example 1, according to the patent "A low-temperature molten salt electrolysis clean metallurgical method and device (Chinese Patent 201710775124.0)" The plan is to carry out a molten salt electrolysis test. The difference is that the electrolysis cycle is extended to 12 hours, and the amount of feed during the electrolysis process is the same as in Example 1. After the test, calculated based on the crude antimony obtained, the current efficiency was 65.23%, the electrolysis energy consumption was 3.86kWh·kg -1 , and the antimony content in the slag was 1.58%.
对比例3Comparative example 3
此对比例为高锑电解炉和贫化电解炉电解温度相同方案：同上述实施例1相同原料，称取硫化锑与熔盐质量百分比为5:1的混合物料，依次置于高锑电解炉中，开启热电阻升高温度至900℃，调整电极间距为4cm，开启气体喷枪控制气体压力为0.15Mpa，流量为185 L/(min·m 3)。启动电源设置电流密度大小为2100 A·m -2，限槽电压为3.8V，按照理论消耗量持续补料，电解9h后，放出粗锑，收集含硫烟尘，其余的高锑电解炉熔体经过溜槽进入贫化电解炉，并补充熔盐20%（以高锑电解炉出来的熔体为基准计算），电解炉内温度控制在900℃，接通电源槽电压控制为3 V，电解3h后停止电解，静止分层后，依次从放锑口、排渣口放出粗锑、熔盐与炉渣，从烟气口收集含硫烟尘。电解炉的全流程电流效率为86.8%，电解能耗为3.15kWh·kg -1，电解残渣中含锑1.21%。 This comparative example is the same electrolysis temperature solution for the high antimony electrolytic furnace and the depleted electrolytic furnace: the same raw materials as in the above example 1, weigh a mixture of antimony sulfide and molten salt with a mass percentage of 5:1, and place it in the high antimony electrolytic furnace in sequence. , turn on the thermal resistor to increase the temperature to 900°C, adjust the electrode spacing to 4cm, turn on the gas spray gun to control the gas pressure to 0.15Mpa, and the flow rate to 185 L/(min·m 3 ). Start the power supply and set the current density to 2100 A·m -2 and the cell voltage limit to 3.8V. Continue to replenish materials according to the theoretical consumption. After 9 hours of electrolysis, release the crude antimony, collect sulfur-containing smoke and dust, and the remaining high antimony electrolytic furnace melt Enter the depletion electrolytic furnace through the chute, and add 20% molten salt (calculated based on the melt coming out of the high antimony electrolytic furnace). The temperature in the electrolytic furnace is controlled at 900°C. The voltage of the power tank is turned on and controlled at 3 V. Electrolysis lasts for 3 hours. Finally, the electrolysis is stopped. After static stratification, crude antimony, molten salt and slag are discharged from the antimony discharge port and slag discharge port in sequence, and sulfur-containing smoke and dust are collected from the flue gas port. The entire process current efficiency of the electrolysis furnace is 86.8%, the electrolysis energy consumption is 3.15kWh·kg -1 , and the electrolysis residue contains 1.21% antimony.
对比例4Comparative example 4
此对比例为高锑电解炉和贫化电解炉均采用恒电流方案：同上述实施例1相同原料，称取硫化锑与熔盐质量百分比为5:1的混合物料，依次置于高锑电解炉中，开启热电阻升高温度至900℃，调整电极间距为4cm，开启气体喷枪控制气体压力为0.15Mpa，流量为185 L/(min·m 3)。启动电源设置电流密度大小为2100 A·m -2，限槽电压为3.8V，按照理论消耗量持续补料，电解9h后，放出粗锑，收集含硫烟尘，其余的高锑电解炉熔体经过溜槽进入贫化电解炉，并补充熔盐20%（以高锑电解炉出来的熔体为基准计算），电解炉内温度控制在950℃，接通电源设置电流密度大小为2100 A·m -2，电解3h后停止电解，静止分层后，依次从放锑口、排渣口放出粗锑、熔盐与炉渣，从烟气口收集含硫烟尘。电解炉的全流程电流效率为54.8%，电解能耗为8.15kWh·kg -1，电解残渣中含锑0.32%。 This comparative example uses a constant current scheme for both the high antimony electrolytic furnace and the depleted electrolytic furnace: the same raw materials as in Example 1 above, weigh a mixture of antimony sulfide and molten salt with a mass percentage of 5:1, and place them in the high antimony electrolysis furnace in sequence. In the furnace, turn on the thermal resistor to increase the temperature to 900°C, adjust the electrode spacing to 4cm, turn on the gas spray gun to control the gas pressure to 0.15Mpa, and the flow rate to 185 L/(min·m 3 ). Start the power supply and set the current density to 2100 A·m -2 and the cell voltage limit to 3.8V. Continue to replenish materials according to the theoretical consumption. After 9 hours of electrolysis, release the crude antimony, collect sulfur-containing smoke and dust, and the remaining high antimony electrolytic furnace melt Enter the depleted electrolytic furnace through the chute, and add 20% molten salt (calculated based on the melt coming out of the high antimony electrolytic furnace). The temperature in the electrolytic furnace is controlled at 950°C. The power is turned on and the current density is set to 2100 A·m. -2 . Stop electrolysis after 3 hours of electrolysis. After static stratification, release crude antimony, molten salt and slag from the antimony discharge port and slag discharge port in sequence, and collect sulfur-containing smoke and dust from the flue gas port. The full-process current efficiency of the electrolysis furnace is 54.8%, the electrolysis energy consumption is 8.15kWh·kg -1 , and the electrolysis residue contains 0.32% antimony.

Claims (10)

  1. 一种硫化锑矿熔盐电解连续化生产的方法，其特征在于，包括以下步骤：A method for continuous electrolysis production of antimony sulfide ore molten salt, which is characterized by including the following steps:
    （1）将硫化锑矿和共晶熔盐置于高锑电解炉内进行恒电流限压升温电解熔炼，熔炼过程中吹入惰性气体搅动熔体，金属锑液和单质硫分别从高锑电解炉的放锑口、高锑电解炉的烟气口排出；(1) Place antimony sulfide ore and eutectic molten salt in a high antimony electrolytic furnace for constant current, limited voltage and temperature rise electrolytic smelting. During the smelting process, inert gas is blown into the melt to stir the melt, and the metallic antimony liquid and elemental sulfur are electrolyzed from high antimony respectively. The antimony discharge port of the furnace and the smoke port of the high antimony electrolytic furnace are discharged;
    （2）将步骤（1）得到的电解后熔体通过溜槽进入贫化电解炉内进行恒电压贫化电解，电解前补充熔盐，金属锑液和单质硫分别从贫化电解炉的放锑口、贫化电解炉的烟气口排出，贫化后渣由排渣口放出。(2) Enter the electrolyzed melt obtained in step (1) through the chute into the depletion electrolytic furnace for constant voltage depletion electrolysis. Before electrolysis, replenish molten salt, metallic antimony liquid and elemental sulfur to discharge antimony from the depletion electrolytic furnace respectively. The flue gas port of the depleted electrolytic furnace is discharged, and the depleted slag is released from the slag discharge port.
  2. 根据权利要求1所述的方法，其特征在于，步骤（1）中，硫化锑矿与共晶熔盐的质量百分比为10:1～5:4，优选为6:1～5:2；共晶熔盐为氯化钠和氯化钾的混合物，氯化钠与氯化钾的质量百分比为7:3～2:7，优选为4:5～2:5。The method according to claim 1, characterized in that, in step (1), the mass percentage of antimony sulfide ore and eutectic molten salt is 10:1 to 5:4, preferably 6:1 to 5:2; the eutectic The molten salt is a mixture of sodium chloride and potassium chloride, and the mass percentage of sodium chloride and potassium chloride is 7:3 to 2:7, preferably 4:5 to 2:5.
  3. 根据权利要求1所述的方法，其特征在于，步骤（1）中，高锑电解熔炼时炉内温度为700～950℃，优选为850～900℃；阳极电流密度为1000～5000 A·m -2，优选为2000～3000 A·m -2；槽电压控制在4 V以下，优选控制在3.8 V以下；阴阳极间距为1～8cm，优选为2～4cm。 The method according to claim 1, characterized in that in step (1), the temperature in the furnace during high antimony electrolytic smelting is 700-950°C, preferably 850-900°C; the anode current density is 1000-5000 A·m -2 , preferably 2000-3000 A·m -2 ; the cell voltage is controlled below 4 V, preferably below 3.8 V; the cathode-anode spacing is 1-8cm, preferably 2-4cm.
  4. 根据权利要求1所述的方法，其特征在于，步骤（1）中，惰性气体吹入前需预热，优选预热气体温度为700～950℃；惰性气体优选为氮气或氩气，吹入惰性气体的压力为0.12～0.35MPa，惰性气体流量为40～1100 L/(min·m 3)。 The method according to claim 1, characterized in that, in step (1), the inert gas needs to be preheated before blowing, and the preferred preheated gas temperature is 700-950°C; the inert gas is preferably nitrogen or argon, and the inert gas is blown into The pressure of the inert gas is 0.12~0.35MPa, and the flow rate of the inert gas is 40~1100 L/(min·m 3 ).
  5. 根据权利要求1所述的方法，其特征在于，步骤（1）中，高锑电解熔炼反应时间为2～20h，优选为8～15h。The method according to claim 1, characterized in that in step (1), the high antimony electrolytic smelting reaction time is 2 to 20 hours, preferably 8 to 15 hours.
  6. 根据权利要求1所述的方法，其特征在于，步骤（2）中，贫化电解前补充的熔盐为共晶熔盐，熔盐补充量为5～40%。The method according to claim 1, characterized in that in step (2), the molten salt supplemented before the depletion electrolysis is eutectic molten salt, and the molten salt supplementary amount is 5 to 40%.
  7. 根据权利要求1所述的方法，其特征在于，步骤（2）中，贫化电解炉内温度为700～1050℃，优选为850～950℃；贫化电解时槽电压为1.5～4.5 V，优选为2.5～3.5 V；阴阳极间距为1～8cm，优选为2～4cm。The method according to claim 1, characterized in that in step (2), the temperature in the depletion electrolysis furnace is 700-1050°C, preferably 850-950°C; the cell voltage during depletion electrolysis is 1.5-4.5 V, Preferably it is 2.5~3.5 V; the distance between cathode and anode is 1~8cm, preferably 2~4cm.
  8. 根据权利要求1所述的方法，其特征在于，步骤（2）中，贫化电解反应时间为2～6h，优选为3～4h。The method according to claim 1, characterized in that in step (2), the depletion electrolysis reaction time is 2 to 6 hours, preferably 3 to 4 hours.
  9. 权利要求1-8任一项所述的硫化锑矿熔盐电解连续化生产的方法配套的装置，其特征在于，包括结构相同的两个电解炉，所述的电解炉包括中空的炉体和设置于炉体内的电解单元；所述的炉体在上部分别设有入料口和烟气口，在下部分别设有放锑口和排渣口；其中一个电解炉作为高锑电解炉，且排渣口的位置高于另一个作为贫化电解炉的入料口，高锑电解炉的排渣口通过溜槽连接至贫化电解炉的入料口；高锑电解炉还设有伸入至炉体内吹入惰性气体的气体喷枪。The device supporting the method for continuous electrolysis production of antimony sulfide ore molten salt according to any one of claims 1 to 8, characterized in that it includes two electrolytic furnaces with the same structure, and the electrolytic furnace includes a hollow furnace body and An electrolysis unit is provided in the furnace body; the furnace body is provided with a feeding port and a flue gas port respectively on the upper part, and an antimony discharging port and a slag discharging port respectively on the lower part; one of the electrolytic furnaces is used as a high antimony electrolytic furnace, and The position of the slag discharge port is higher than the other feed port of the depletion electrolytic furnace. The slag discharge port of the high antimony electrolytic furnace is connected to the feed port of the depletion electrolytic furnace through a chute; the high antimony electrolytic furnace also has a structure extending into A gas lance that blows inert gas into the furnace body.
  10. 根据权利要求9所述的装置，其特征在于，电解炉的外壁上设有热电阻，且热电阻外包覆有保温层；所述溜槽设有放料阀门和取样观测口，溜槽内熔体的流动速度为0.1～0.8 m·s -1； The device according to claim 9, characterized in that a thermal resistor is provided on the outer wall of the electrolysis furnace, and the thermal resistor is covered with an insulation layer; the chute is provided with a discharge valve and a sampling observation port, and the melt in the chute is The flow speed is 0.1～0.8 m·s -1 ;
    所述的电解单元包括设置于炉体内底部的阴极和设置于炉体上部的阳极，所述的阳极连接伸出至炉体外的阳极导杆，以通过导线连接电源正极；所述的阴极通过导线连接电源负极。The electrolysis unit includes a cathode arranged at the bottom of the furnace body and an anode arranged at the upper part of the furnace body. The anode is connected to an anode guide rod extending out of the furnace body to connect the positive electrode of the power supply through a wire; the cathode is connected through a wire Connect the negative terminal of the power supply.
PCT/CN2023/093924 2022-06-20 2023-05-12 Antimony-sulfide-containing ore-based molten salt electrolysis continuous production method and apparatus WO2023246367A1 (en)

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