A device and method for comprehensive utilization of sphalerite

Abstract

A kind of sphalerite multi-element comprehensive utilization device and method, belong to sphalerite comprehensive utilization technical field, the device includes spiral propelling condenser;The spiral propelling condenser is mainly by stirring motor, spiral propelling stirring paddle, flue gas import, discharge airlock, flue gas export, tank body portion is constituted;The method includes: 1) sphalerite, hydrogen, alkali base oxide reduction reaction occurs, the metal component in sphalerite is reduced into metal element, sulfur is converted into alkali base sulfide;2) solid product alkali base sulfide is oxidized to obtain alkali base sulfate using its waste heat;Or, solid product alkali base sulfide is converted into hydrogen sulfide and alkali with water, hydrogen sulfide catalytic electrolysis obtains elemental sulfur and hydrogen, hydrogen is recycled for the first stage reduction, sulfur as product;3) zinc is in the form of zinc steam with flue gas and is taken out of the reaction system, and is condensed in spiral propelling condenser and is recycled;4) the obtained product after reaction is magnetically separated, and elemental iron powder is obtained.

Description

Technical Field

[0001] This invention belongs to the field of comprehensive utilization technology of sphalerite, specifically relating to a device and method for comprehensive utilization of multiple elements in sphalerite. Background Technology

[0002] Sphalerite is the richest zinc mineral, accounting for about 90% of total zinc production. When sphalerite contains more than 6% iron, it is called ferrosphalerite. Currently, the main methods for extracting valuable components from sphalerite are pyrometallurgy and hydrometallurgy. Pyrometallurgy is currently more commonly used, as it requires high ore grades and also causes significant environmental pollution.

[0003] Patent CN201811052107.5 discloses a method for extracting zinc from low-grade lead-zinc ore. The apparatus used in this extraction method includes a connected reduction smelting unit and a dust collection unit. The total lead and zinc content in the low-grade lead-zinc ore is less than 20 wt%, and the zinc and lead elements exist in a symbiotic form as zinc silicate, zinc carbonate, zinc sulfide, lead carbonate, and lead sulfide. The extraction method includes: subjecting the low-grade lead-zinc ore, reducing fuel, and cerussite to a reduction smelting reaction to obtain zinc oxide dust and lead-containing slag. Compared to the preparation of metallic zinc and lead from other raw materials, this invention uses low-grade oxidized lead-zinc ore as raw material, resulting in lower production costs. During the reduction smelting process, zinc sulfide in the raw material undergoes a redox reaction with lead oxide, enriching and separating the zinc element from the low-grade oxidized lead-zinc ore in the form of high-grade zinc oxide dust, effectively separating the zinc and lead elements from the original ore.

[0004] Patent CN201410255424.2 provides a method for extracting zinc from zinc sulfide concentrate by a combination of roasting and leaching and direct leaching. The method includes the following steps: (1) neutral leaching of zinc sulfide concentrate to obtain zinc roasted sand by roasting and acidification, with a leaching temperature of 60-70℃ and an endpoint pH of 5.0-5.2; (2) hot acid leaching of the underflow from the neutral leaching in step (1), with a leaching temperature of 80-90℃ and an endpoint acidity of 50-100 g / L; (3) adding zinc sulfide concentrate to the supernatant from the hot acid leaching in step (2), introducing oxygen with a concentration of 98% or higher, and simultaneously leaching zinc and removing iron under the conditions of a temperature of 145-155℃, a pressure of 1100-1300 kPa, and an endpoint acidity of 10-20 g / L.

[0005] Patent CN200710066183.7 provides a vacuum integrated smelting method for high-iron sphalerite concentrate, which includes the following steps: (1) mixing high-iron sphalerite concentrate and copper, adding it into a vacuum reactor, and forming mZnS under high temperature and vacuum conditions. nFeS melt, i.e. zinc matte; (2) under copper catalysis, zinc sulfide in zinc matte is converted into cuprous sulfide and forms a copper-sulfur-iron alloy with ferrous sulfide, i.e. matte. Zinc and some associated metals are displaced and extracted in vapor form, realizing the separation of zinc from iron and sulfur. The remaining rare metals are enriched in matte and will be further enriched and extracted in the next step; (3) Zinc vapor is condensed into liquid or solid in a special condenser to obtain crude zinc; (4) Quartz is mixed into the produced matte and then enters the blowing furnace. The sulfur in the matte is oxidized to produce high-temperature sulfur dioxide flue gas, which is used to produce sulfuric acid. A large amount of heat generated is recovered by a waste heat recovery boiler. Ferrous sulfide and quartz form harmless ferric silicate slag, and cuprous sulfide forms crude copper. The zinc and some valuable metals remaining during the blowing process are oxidized and enter the gas phase as dust. After dust collection, they are comprehensively recovered, while the precious metals are enriched in the crude copper and extracted from the crude copper.

[0006] It is evident that existing methods for utilizing sphalerite mostly employ pyrometallurgical roasting, and the inability to directly utilize the low-concentration SO2 flue gas during the roasting process has become a key issue hindering the clean utilization of sphalerite. Summary of the Invention

[0007] To address the aforementioned problems, the purpose of this invention is to provide a device and method for the comprehensive utilization of multiple elements in sphalerite.

[0008] A multi-element comprehensive utilization device for sphalerite includes a multi-stage cyclone heat exchanger and a spiral propulsion condenser. The spiral propulsion condenser mainly consists of a stirring motor, a spiral propulsion agitator, a flue gas inlet, a discharge airlock, a flue gas outlet, and a tank body. Figure 2 The spiral propeller agitator, discharge airlock, and flue gas outlet are connected to the tank body via flanges. The flue gas outlet is connected to the shaft of the spiral propeller agitator and is located at the top of the tank body. The shaft of the spiral propeller agitator has a hollow structure, and the remaining flue gas after condensation is discharged through the axial flue gas outlet. The discharge airlock is located at the bottom of the tank body. The flue gas inlet is located on the upper side of the tank body. The spiral propeller agitator rotates under the action of the agitator motor, and the propulsion speed of the spiral propeller agitator is 10~100rpm, pushing the condensed product towards the bottom discharge airlock. The discharge airlock ensures that the condensed product is discharged in one direction. This prevents zinc powder from adhering to the wall surface during condensation, ensures continuous discharge and packaging of zinc powder, and achieves a zinc powder condensation recovery efficiency of greater than 99%.

[0009] A method for the comprehensive utilization of multiple elements in sphalerite, implemented using the aforementioned apparatus, such as... Figure 1 As shown, it includes the following steps:

[0010] (1) Using sphalerite as raw material, hydrogen as reducing agent, and basic oxides as promoter, a multi-stage countercurrent cyclone is used to carry out a reduction reaction, reducing the metal components in sphalerite to metal elements and converting sulfur into basic sulfides.

[0011] (2) Basic sulfides in the solid products generated by the multi-stage cyclone heat exchanger are oxidized by their own waste heat to obtain basic sulfates;

[0012] or

[0013] In the solid products generated by the multi-stage cyclone heat exchanger, basic sulfides are converted into hydrogen sulfide and alkali with water. Hydrogen sulfide is catalytically electrolyzed to obtain elemental sulfur (sulfur) and hydrogen. The hydrogen is recycled for the first stage of reduction, and sulfur is used as a product.

[0014] (3) During the basic hydrogen reduction process, zinc is carried out of the reaction system in the form of zinc vapor and is condensed and recovered in a spiral propulsion condenser;

[0015] (4) The product obtained after the reaction is separated by magnetic separation to obtain elemental iron powder.

[0016] In step (1), sphalerite refers to a mineral containing zinc sulfide; the basic oxide is one of a calcium-based compound, a sodium-based compound, or a potassium-based compound. The amount of basic oxide added is calculated as 1 to 3 times the stoichiometric coefficient of the basic metal and sulfur in the sphalerite in the basic hydrogen reduction reaction, and is converted into the amount of basic oxide added.

[0017] In step (1), the reaction temperature of the base hydrogen reduction reaction is 800-1300℃ and the reaction time is 10-90min.

[0018] In step (1), a multi-stage countercurrent cyclone separator is used as the reaction device. According to the actual needs of the basic hydrogen reduction reaction, a 2-N multi-stage countercurrent cyclone separator is used. In the multi-stage countercurrent cyclone separator, the solid phase and the gas phase are carried out in a countercurrent manner during the heat exchange process.

[0019] Taking a three-stage counter-current cyclone separator as an example, sphalerite and basic oxides are fed into a first-stage counter-current cyclone heat exchanger using high-temperature flue gas generated by a second-stage counter-current cyclone heat exchanger, where heat exchange and basic hydrogen reduction reactions occur. The slag produced by the first-stage counter-current cyclone heat exchanger is fed into a second-stage counter-current cyclone heat exchanger using high-temperature flue gas generated by a third-stage counter-current cyclone heat exchanger, where heat exchange and basic hydrogen reduction reactions occur. The slag produced by the second-stage counter-current cyclone heat exchanger is fed into a third-stage counter-current cyclone heat exchanger using high-temperature hydrogen generated by a hydrogen preheater, where heat exchange and basic hydrogen reduction reactions occur. The slag produced by the third-stage counter-current cyclone heat exchanger is discharged after heat exchange. Compared with conventional fluidized bed reactors, the system's heat utilization rate reaches over 70%, and the hydrogen utilization efficiency reaches over 99%.

[0020] In step (1), the basic hydrogen reduction reaction can also be carried out using a gas-solid reactor including a multi-hearth reduction furnace, a polymer-stirred fluidized bed, and a moving bed. The multi-hearth hydrogen reduction furnace and the continuous packed bed are equipped with a feed airlock at the top and a discharge airlock at the bottom. The feed airlock and the discharge airlock are used to achieve continuous reduction reaction. The polymer-stirred fluidized bed is equipped with a top stirring paddle and a side stirring paddle. The top stirring shaft uses centrifugal force to separate fine particles back into the bed to prevent small particles from escaping. The internal structure of the side stirring shaft is hollow to ensure that solid particles enter the fluidized bed from the bottom of the stirring paddle. The fluidized bed is designed without a sieve plate. Compared with conventional fluidized beds, the large bubble rate is reduced by more than 60%, the heat transfer efficiency is increased by more than 30%, and the dust rate is reduced by less than 2%, preventing the metal powder generated during reduction from sticking together.

[0021] In step (2), the basic sulfides in the solid product generated by the multi-stage cyclone heat exchanger are oxidized by their own residual heat to obtain basic sulfates. The temperature of the solid product is maintained at 20-300℃, and the oxidation time is 10-120 min. After the reaction is completed, the S in the obtained solid product is... 2- Content ≤0.1%; the basic sulfides in the solid products produced by the multi-stage cyclone heat exchanger can also be converted into hydrogen sulfide and alkali with water. Hydrogen sulfide is catalytically electrolyzed to obtain elemental sulfur (sulfur) and hydrogen. The hydrogen is recycled for the first stage reduction, and sulfur is used as a product.

[0022] In step (3), during the basic hydrogen reduction process, zinc is carried out of the reaction system in the form of zinc vapor with the flue gas and is condensed and recovered in a spiral propulsion condenser, with a zinc recovery rate of more than 95%.

[0023] In step (4), the material obtained after the reaction is separated and recovered as elemental iron powder by magnetic separation. The magnetic separation intensity is 0.1 to 1T, and the iron recovery rate is greater than 95%. Basic sulfate and silicon-containing compounds are used as building materials.

[0024] This invention discloses a method for the comprehensive utilization of multiple elements in zinc sphalerite. Taking calcium oxide as an example, the chemical reaction formula of the reaction process includes:

[0025] Base hydrogen reduction process:

[0026] ZnS + CaO + H2(g) = Zn + CaS + H2O(g)

[0027] FeS2 + 2CaO + 2H2(g) = Fe + 2CaS + 2H2O(g)

[0028] Calcium sulfide conversion process

[0029] (1) Low-temperature oxidation reaction:

[0030] CaS + 2O2(g) = CaSO4

[0031] (2) Water conversion and electrolysis reaction:

[0032] CaS + H₂O = H₂S(g) + Ca(OH)₂

[0033] H₂S(g) = H₂(g) + S (Catalytic electrolysis)

[0034] The present invention provides a multi-element comprehensive utilization device and method for sphalerite, which, compared with the prior art, has the following advantages:

[0035] (1) Using an alkaline hydrogen reduction reaction, the metallic components in sphalerite are reduced to elemental metals. Iron powder is recovered by magnetic separation, and zinc powder is melted to obtain zinc ingots. Sulfur is converted into alkaline sulfides, which are then oxidized at low temperature to obtain alkaline sulfates. The alkaline sulfides can also be converted into hydrogen sulfide and alkali with water. Hydrogen sulfide is catalytically electrolyzed to obtain elemental sulfur and hydrogen. The hydrogen is recycled for the first stage of reduction, and sulfur is used as a product. This improves the utilization value of sphalerite.

[0036] (2) SO2 flue gas pollution and sulfuric acid treatment problems are eliminated. This invention uses an alkaline hydrogen reduction reaction to convert sulfur in sphalerite into alkaline sulfides that enter the solid phase. The alkaline sulfides are then oxidized at low temperature to alkaline sulfates, thereby achieving the purpose of sulfur fixation and eliminating environmental pollution problems.

[0037] (3) The present invention uses a spiral propulsion agitator that rotates under the action of a stirring motor, pushing the condensed product toward the bottom discharge airlock. The discharge airlock ensures that the condensed product is discharged in one direction. This prevents zinc powder from adhering to the wall surface during condensation, ensuring continuous discharge and packaging of zinc powder. The condensation recovery efficiency of zinc powder is greater than 99%. Attached Figure Description

[0038] Figure 1 A schematic diagram of a method and apparatus for the comprehensive utilization of multiple elements in sphalerite;

[0039] Figure 2 Schematic diagram of a spiral propulsion condenser device; In the diagram: 1-stirring motor; 2-spiral propulsion agitator; 3-flue gas inlet; 4-discharge airlock; 5-tank body; 6-flue gas outlet. Detailed Implementation

[0040] The present invention will be further described in detail below with reference to the embodiments.

[0041] The embodiments of this invention use zinc sphalerite whose main components are Zn 48%, Fe 12.98%, S 30.62%, with the balance being other components. The basic oxide used is one of calcium oxide, sodium oxide, or potassium oxide.

[0042] Example 1

[0043] A multi-element comprehensive utilization device for sphalerite includes a multi-stage cyclone heat exchanger and a spiral propulsion condenser, wherein, for example... Figure 2 As shown, the spiral propulsion condenser mainly consists of a stirring motor 1, a spiral propulsion agitator 2, a flue gas inlet 3, a discharge airlock 4, a flue gas outlet 6, and a tank body 5. The spiral propulsion agitator 2, discharge airlock 4, and flue gas outlet 6 are connected to the tank body 5 via flanges. The flue gas outlet 6 is connected to the shaft of the spiral propulsion agitator 2 and is located at the top of the tank body 5. The shaft of the spiral propulsion agitator 2 has a hollow structure, and the remaining flue gas after condensation is discharged through the axial flue gas outlet 6. The discharge airlock 4 is located at the bottom of the tank body 5. The flue gas inlet 3 is located on the upper side of the tank body. The spiral propulsion agitator 2 rotates under the action of the stirring motor 1, and the propulsion speed of the spiral propulsion agitator 2 is 10-100 rpm, pushing the condensed product towards the bottom discharge airlock 4. The discharge airlock 4 ensures unidirectional discharge of the condensed product. This prevents zinc powder from adhering to the wall surface during condensation and ensures continuous discharge and encapsulation of zinc powder.

[0044] A method for comprehensive utilization of multiple elements in sphalerite, implemented using the aforementioned apparatus, comprises the following operational steps:

[0045] (1) Mix sphalerite and calcium oxide in a certain proportion, and add calcium oxide in an amount equal to 1 times the stoichiometric coefficient of calcium and sulfur in the basic hydrogen reduction reaction of sphalerite.

[0046] (2) The high-temperature flue gas generated by the secondary counter-current cyclone heat exchanger for sphalerite and basic oxides is fed into the primary counter-current cyclone heat exchanger, where heat exchange and basic hydrogen reduction reactions occur. The slag generated by the primary counter-current cyclone heat exchanger is fed into the secondary counter-current cyclone heat exchanger using the high-temperature flue gas generated by the tertiary counter-current cyclone heat exchanger, where heat exchange and basic hydrogen reduction reactions occur. The slag generated by the secondary counter-current cyclone heat exchanger is fed into the tertiary counter-current cyclone heat exchanger using the high-temperature hydrogen generated by the hydrogen preheater, where heat exchange and basic hydrogen reduction reactions occur. The slag generated by the tertiary counter-current cyclone heat exchanger is discharged after heat exchange. Compared with conventional fluidized bed reactors, the system's heat utilization rate reaches over 70%, and the hydrogen utilization efficiency reaches over 99%. The basic hydrogen reduction process is carried out at a reaction temperature of 800℃ and a reaction time of 90 min.

[0047] (3) Calcium sulfide in the solid product generated by the three-stage cyclone heat exchanger is preheated and oxidized to obtain calcium sulfate. The solid product temperature is 20℃ and the oxidation time is 120min. After the reaction is completed, the S in the material obtained after sorting is... 2－ The content is 0.1%;

[0048] (4) During the basic hydrogen reduction process, zinc is carried out of the reaction system in the form of zinc vapor with the flue gas and is condensed and recovered in the zinc condenser. The zinc vapor condenser adopts a spiral propeller condenser to cool down to a temperature range of 460~520℃. The spiral propeller condenser is driven by a spiral propeller agitator with a stirring speed of 10rpm, which pushes the zinc out through the discharge airlock and seals it. The separation efficiency of flue gas and zinc powder is 99%, and the zinc recovery rate is greater than 95%.

[0049] (5) The materials obtained after the reaction are sorted and separated to recover the metal elements. The magnetic field strength is 0.1T. The iron recovery rate is 95%. Basic sulfates and silicon-containing compounds are used as building materials.

[0050] Example 2

[0051] A method for comprehensive utilization of multiple elements in sphalerite, implemented using the apparatus of Example 1, comprises the following operational steps:

[0052] (1) Mix sphalerite and sodium oxide in a certain proportion, and add sodium oxide in an amount equal to 1 times the stoichiometric coefficient of calcium and sulfur in the basic hydrogen reduction reaction of sphalerite;

[0053] (2) The high-temperature flue gas generated by the secondary counter-current cyclone heat exchanger for sphalerite and basic oxides is fed into the primary counter-current cyclone heat exchanger, where heat exchange and basic hydrogen reduction reactions occur. The slag generated by the primary counter-current cyclone heat exchanger is fed into the secondary counter-current cyclone heat exchanger using the high-temperature flue gas generated by the tertiary counter-current cyclone heat exchanger, where heat exchange and basic hydrogen reduction reactions occur. The slag generated by the secondary counter-current cyclone heat exchanger is fed into the tertiary counter-current cyclone heat exchanger using the high-temperature hydrogen generated by the hydrogen preheater, where heat exchange and basic hydrogen reduction reactions occur. The slag generated by the tertiary counter-current cyclone heat exchanger is discharged after heat exchange. Compared with conventional fluidized bed reactors, the system's heat utilization rate reaches over 70%, and the hydrogen utilization efficiency reaches over 99%. The basic hydrogen reduction process is carried out at a reaction temperature of 1200℃ and a reaction time of 10 min.

[0054] (3) Sodium sulfide in the solid product generated by the three-stage cyclone heat exchanger is oxidized by its own preheating to obtain sodium sulfate. The solid product temperature is 200℃ and the oxidation time is 40min. After the reaction is completed, the S in the material obtained after sorting is... 2－ The content is 0.07%;

[0055] (4) During the basic hydrogen reduction process, zinc is carried out of the reaction system in the form of zinc vapor with the flue gas and is condensed and recovered in the zinc condenser. The zinc vapor condenser adopts a spiral propeller condenser to cool down to a temperature range of 460~520℃. The spiral propeller condenser is driven by a spiral propeller agitator with a stirring speed of 100rpm, which pushes the zinc out through the discharge airlock and seals it. The separation efficiency of flue gas and zinc powder is 99%, and the zinc recovery rate is greater than 96%.

[0056] (5) The materials obtained after the reaction are sorted and separated to recover the metal elements. The magnetic field strength is 0.4T and the iron recovery rate is 97%. Basic sulfates and silicon-containing compounds are used as building materials.

[0057] Example 3

[0058] A method for comprehensive utilization of multiple elements in sphalerite, implemented using the apparatus of Example 1, comprises the following operational steps:

[0059] (1) Mix sphalerite and potassium oxide in a certain proportion, and add potassium oxide in an amount that is 1.5 times the stoichiometric coefficient of calcium and sulfur in the basic hydrogen reduction reaction of sphalerite.

[0060] (2) The high-temperature flue gas generated by the secondary counter-current cyclone heat exchanger for zinc sphalerite and potassium oxide is fed into the primary counter-current cyclone heat exchanger, where heat exchange and basic hydrogen reduction reactions occur. The slag generated by the primary counter-current cyclone heat exchanger is fed into the secondary counter-current cyclone heat exchanger using the high-temperature flue gas generated by the tertiary counter-current cyclone heat exchanger, where heat exchange and basic hydrogen reduction reactions occur. The slag generated by the secondary counter-current cyclone heat exchanger is fed into the tertiary counter-current cyclone heat exchanger using the high-temperature hydrogen generated by the hydrogen preheater, where heat exchange and basic hydrogen reduction reactions occur. The slag generated by the tertiary counter-current cyclone heat exchanger is discharged after heat exchange. Compared with conventional fluidized bed reactors, the system's heat utilization rate reaches over 70%, and the hydrogen utilization efficiency reaches over 99%. The basic hydrogen reduction process is carried out at a reaction temperature of 800℃ for a reaction time of 20 min.

[0061] (3) Potassium sulfide in the solid product generated by the three-stage cyclone heat exchanger is preheated and oxidized to potassium sulfate. The solid product temperature is 120℃ and the oxidation time is 40min. After the reaction is completed, the S in the material obtained after sorting is... 2－ The content is 0.07%;

[0062] (4) During the basic hydrogen reduction process, zinc is carried out of the reaction system in the form of zinc vapor with the flue gas and is condensed and recovered in the zinc condenser. The zinc vapor condenser adopts a spiral propeller condenser to cool down to a temperature range of 460~520℃. The spiral propeller condenser is driven by a spiral propeller agitator with a stirring speed of 80rpm, which pushes the zinc out through the discharge airlock and seals it. The separation efficiency of flue gas and zinc powder is 99%, and the zinc recovery rate is greater than 96%.

[0063] (5) The materials obtained after the reaction are sorted and separated to recover the metal elements. The magnetic field strength is 0.7T and the iron recovery rate is 95%. Basic sulfates and silicon-containing compounds are used as building materials.

[0064] Example 4

[0065] A method for comprehensive utilization of multiple elements in sphalerite, implemented using the apparatus of Example 1, comprises the following operational steps:

[0066] (1) Mix sphalerite and calcium oxide in a certain proportion, and add calcium oxide in an amount that is twice the stoichiometric coefficient of calcium and sulfur in the basic hydrogen reduction reaction of sphalerite.

[0067] (2) The high-temperature flue gas generated by the secondary counter-current cyclone heat exchanger for sphalerite and calcium oxide is fed into the primary counter-current cyclone heat exchanger, where heat exchange and basic hydrogen reduction reactions occur. The slag generated by the primary counter-current cyclone heat exchanger is fed into the secondary counter-current cyclone heat exchanger using the high-temperature flue gas generated by the tertiary counter-current cyclone heat exchanger, where heat exchange and basic hydrogen reduction reactions occur. The slag generated by the secondary counter-current cyclone heat exchanger is fed into the tertiary counter-current cyclone heat exchanger using the high-temperature hydrogen generated by the hydrogen preheater, where heat exchange and basic hydrogen reduction reactions occur. The slag generated by the tertiary counter-current cyclone heat exchanger is discharged after heat exchange. Compared with conventional fluidized bed reactors, the system's heat utilization rate reaches over 70%, and the hydrogen utilization efficiency reaches over 99%. The basic hydrogen reduction process is carried out at a reaction temperature of 900℃ and a reaction time of 30 min.

[0068] (3) Calcium sulfide in the solid product generated by the three-stage cyclone heat exchanger is preheated and oxidized to obtain calcium sulfate. The solid product temperature is 100℃ and the oxidation time is 60min. After the reaction is completed, the S in the material obtained after sorting is... 2－ The content is 0.08%;

[0069] (4) During the basic hydrogen reduction process, zinc is carried out of the reaction system in the form of zinc vapor with the flue gas and is condensed and recovered in the zinc condenser. The zinc vapor condenser adopts a spiral propeller condenser to cool down to a temperature range of 460~520℃. The spiral propeller condenser is driven by a spiral propeller agitator with a stirring speed of 60rpm, which pushes the zinc out through the discharge airlock and seals it. The separation efficiency of flue gas and zinc powder is 99%, and the zinc recovery rate is greater than 96%.

[0070] (5) The materials obtained after the reaction are sorted and separated to recover the metal elements. The magnetic field strength is 0.6T. The iron recovery rate is 96%. Basic sulfates and silicon-containing compounds are used as building materials.

[0071] Example 5

[0072] A method for comprehensive utilization of multiple elements in sphalerite, implemented using the apparatus of Example 1, comprises the following operational steps:

[0073] (1) Mix sphalerite and calcium oxide in a certain proportion, and add calcium oxide in an amount that is 3 times the stoichiometric coefficient of calcium and sulfur in the basic hydrogen reduction reaction of sphalerite.

[0074] (2) The high-temperature flue gas generated by the secondary counter-current cyclone heat exchanger for sphalerite and calcium oxide is fed into the primary counter-current cyclone heat exchanger, where heat exchange and basic hydrogen reduction reactions occur. The slag generated by the primary counter-current cyclone heat exchanger is fed into the secondary counter-current cyclone heat exchanger using the high-temperature flue gas generated by the tertiary counter-current cyclone heat exchanger, where heat exchange and basic hydrogen reduction reactions occur. The slag generated by the secondary counter-current cyclone heat exchanger is fed into the tertiary counter-current cyclone heat exchanger using the high-temperature hydrogen generated by the hydrogen preheater, where heat exchange and basic hydrogen reduction reactions occur. The slag generated by the tertiary counter-current cyclone heat exchanger is discharged after heat exchange. Compared with conventional fluidized bed reactors, the system's heat utilization rate reaches over 70%, and the hydrogen utilization efficiency reaches over 99%. The basic hydrogen reduction process is carried out at a reaction temperature of 1300℃ and a reaction time of 40 min.

[0075] (3) The basic sulfides in the solid products produced by the three-stage cyclone heat exchanger can also be converted into hydrogen sulfide and alkali with water. Hydrogen sulfide is catalytically electrolyzed to obtain elemental sulfur (sulfur) and hydrogen. The hydrogen is recycled for the first stage of reduction, and sulfur is used as a product.

[0076] (4) During the basic hydrogen reduction process, zinc is carried out of the reaction system in the form of zinc vapor with the flue gas and is condensed and recovered in the zinc condenser. The zinc vapor condenser adopts a spiral propeller condenser to cool down to a temperature range of 460~520℃. The spiral propeller condenser is driven by a spiral propeller agitator with a stirring speed of 80rpm, which pushes the zinc out through the discharge airlock and seals it. The separation efficiency of flue gas and zinc powder is 99%, and the zinc recovery rate is greater than 96%.

[0077] (5) The materials obtained after the reaction are sorted and separated to recover the metal elements. The magnetic field strength is 1T and the iron recovery rate is 97%. Basic sulfates and silicon-containing compounds are used as building materials.

Claims

1. A method for the comprehensive utilization of multiple elements in sphalerite, characterized in that, A multi-element comprehensive utilization device for sphalerite is adopted. The device includes a multi-stage counter-current cyclone heat exchanger and a spiral propulsion condenser. The spiral propulsion condenser mainly consists of a stirring motor (1), a spiral propulsion stirring paddle (2), a flue gas inlet (3), a discharge airlock (4), a flue gas outlet (6), and a tank body (5). The spiral propulsion stirring paddle (2), the discharge airlock (4), and the flue gas outlet (6) are connected to the tank body (5) by flanges. The flue gas outlet (6) is connected to the spiral propulsion condenser. The propulsion agitator (2) is shaft-connected and located at the top of the tank (5); the shaft of the spiral propulsion agitator (2) is hollow, and the remaining flue gas after condensation is discharged through the axial flue gas outlet (6); the discharge airlock (4) is located at the bottom of the tank; the flue gas inlet (3) is located on the upper side of the tank; the spiral propulsion agitator (2) rotates under the action of the agitator motor (1), pushing the condensed product to move towards the bottom discharge airlock (4), and the discharge airlock (4) ensures that the condensed product is discharged in one direction; including the following steps: (1) Using zinc sphalerite containing zinc sulfide as raw material, hydrogen as reducing agent, and basic oxide as promoter, a multi-stage countercurrent cyclone heat exchanger is used to carry out a reduction reaction, reducing the metal components in the zinc sphalerite to metal elements and converting sulfur into basic sulfides; the basic oxide is one of calcium-based compound, sodium-based compound, or potassium-based compound; the reaction temperature of the basic hydrogen reduction reaction is 800-1300℃ and the reaction time is 10-90min; (2) The basic sulfides in the solid products generated by the multi-stage countercurrent cyclone heat exchanger are oxidized by their own waste heat to obtain basic sulfates. The temperature of the solid products is maintained at 20-300℃ and the oxidation time is 10-120 min. After the reaction is completed, the S in the obtained solid products is... 2- Content ≤0.1%; or In the solid products generated by the multi-stage countercurrent cyclone heat exchanger, basic sulfides are converted into hydrogen sulfide and alkali with water. Hydrogen sulfide is catalytically electrolyzed to obtain elemental sulfur and hydrogen. The hydrogen is recycled for the first stage of reduction, and sulfur is used as a product. (3) During the basic hydrogen reduction process, zinc is carried out of the reaction system in the form of zinc vapor and is condensed and recovered in a spiral propulsion condenser; (4) The product obtained after the reaction is separated by magnetic separation to obtain elemental iron powder.

2. The method for comprehensive utilization of multiple elements in sphalerite according to claim 1, characterized in that, The spiral propulsion agitator (2) has a propulsion and mixing speed of 10~100 rpm.

3. The method for comprehensive utilization of multiple elements in sphalerite according to claim 1, characterized in that, The device can prevent zinc powder from adhering to the tank wall when it condenses, ensuring that zinc powder is continuously discharged and packaged.

4. The method for comprehensive utilization of multiple elements in sphalerite according to claim 1, characterized in that, In step (1), the amount of basic oxide added is calculated as 1 to 3 times the stoichiometric coefficient of the basic metal and sulfur in sphalerite in the basic hydrogen reduction reaction, and is converted into basic oxide.

5. The method for comprehensive utilization of multiple elements in sphalerite according to claim 1, characterized in that, In step (3), during the basic hydrogen reduction process, zinc is carried out of the reaction system in the form of zinc vapor with the flue gas and is condensed and recovered in a spiral propulsion condenser, with a zinc recovery rate of more than 95%.

6. The method for comprehensive utilization of multiple elements in sphalerite according to claim 1, characterized in that, In step (4), the material obtained after the reaction is separated and recovered as elemental iron powder by magnetic separation. The magnetic separation intensity is 0.1 to 1T, and the iron recovery rate is greater than 95%. Basic sulfate and silicon-containing compounds are used as building materials.

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