WO2024060891A1 - 一种复杂粗锡绿色高效的精炼方法 - Google Patents

一种复杂粗锡绿色高效的精炼方法 Download PDF

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WO2024060891A1
WO2024060891A1 PCT/CN2023/113422 CN2023113422W WO2024060891A1 WO 2024060891 A1 WO2024060891 A1 WO 2024060891A1 CN 2023113422 W CN2023113422 W CN 2023113422W WO 2024060891 A1 WO2024060891 A1 WO 2024060891A1
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tin
crude
crude tin
melt
arsenic
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PCT/CN2023/113422
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English (en)
French (fr)
Inventor
宋兴诚
杨斌
王彦坤
刘庆东
陈云
唐都作
袁海滨
徐宝强
李一夫
马士淋
丁剑
徐万立
孔令鑫
熊恒
陈秀敏
杨德香
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云南锡业股份有限公司锡业分公司
昆明理工大学
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Publication of WO2024060891A1 publication Critical patent/WO2024060891A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B25/00—Obtaining tin
    • C22B25/08—Refining
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/005—Preliminary treatment of scrap
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C22B15/0026—Pyrometallurgy
    • C22B15/0028—Smelting or converting
    • C22B15/003—Bath smelting or converting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/02—Obtaining nickel or cobalt by dry processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B30/00—Obtaining antimony, arsenic or bismuth
    • C22B30/02—Obtaining antimony
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B30/00—Obtaining antimony, arsenic or bismuth
    • C22B30/04—Obtaining arsenic
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/02—Refining by liquating, filtering, centrifuging, distilling, or supersonic wave action including acoustic waves
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/04—Refining by applying a vacuum
    • 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 belongs to the technical field of non-ferrous metal pyrometallurgy, and more specifically relates to a green and efficient refining method of complex crude tin.
  • Tin has always played an important role in the process of human civilization and is an indispensable strategic metal supporting high-tech industries and modern industries such as military industry, aerospace, electronic information, and modern photovoltaics.
  • my country's tin reserves are 1.1 million tons, accounting for approximately 23% of global tin reserves; refined tin production is 165,200 tons, accounting for approximately 44% of the world's total production, ranking first in the world for 20 consecutive years; refined tin consumption is 183,700 tons, approximately Accounting for 47% of world consumption.
  • Yunnan province is the core production area of the global tin industry. Gejiu, Yunnan is known as the "Tin Capital" of the world. Yunnan's tin resource reserves are 320,000 tons, ranking first in my country, accounting for approximately 7% of the world's total reserves; refined tin production is 130,000 tons, approximately Accounting for 80% of national production and 35% of global production.
  • the world's tin ore resources are mainly vein tin ores, which have many associated components. Tin ore only accounts for 12% of the single mineral form. Symbiotic and associated minerals usually contain valuable metals such as copper, lead, antimony, bismuth, silver, iron, sulfur, and arsenic; high-quality placer tin ores are mainly concentrated in Southeast Asia, but are also becoming increasingly depleted. As of the end of 2021, the world's total tin resource reserves are 4.9 million tons, of which China, Indonesia, Vietnamese, Australia, and Brazil account for about 73% of the world's reserves. my country's tin ore reserves are highly concentrated, with five provinces and regions, including Yunnan, Guangxi, Hunan, Guangdong, and Inner Mongolia, accounting for more than 85% of the country's reserves.
  • the fire refining process for crude tin mainly includes the following steps: removing iron and arsenic in a reverberatory furnace of ethyl tin, removing iron and arsenic by smelting and condensation of methyl tin, and adding Sulfur removes copper, crystallization removes lead and bismuth, aluminum is added to remove arsenic and antimony, and finally refined tin is produced.
  • Fire refining technology is difficult to remove impurities, has a long process flow, low direct tin recovery rate, high operating costs, and affects product quality. A large amount of refining waste residue that is difficult to process is produced, which poses serious environmental hazards, safety risks and occupational health hazards to employees.
  • Crude tin electrolytic refining technology uses the difference in standard electrode potential between metallic tin and impurity elements to separate and purify the main metal tin from other impurity elements in a specific solution under a certain temperature and DC current.
  • tin precipitates at the cathode, and metals with a more positive potential than tin (antimony, bismuth, arsenic, copper, silver, etc.) remain in the anode mud and are then comprehensively recovered from the anode mud. Since lead and tin have similar potentials, it is difficult to separate them by wet electrolysis.
  • Wet processing technology has higher requirements for crude tin raw materials.
  • the content of impurities copper and iron must be less than 1%, and the total arsenic and antimony content must be less than 1%.
  • This technology first used a perhydrochloric acid electrolyte system, but the crude tin electrolysis temperature was high, and the hydrochloric acid easily volatilized to form acid mist. The production environment was harsh, which caused great harm to the health of production personnel. Later, it switched to a sulfuric acid electrolyte system, but After electrolysis, impurity lead will combine with sulfate ions to form lead sulfate, which will adhere to the anode surface with other insoluble matter to form a solid film, passivating the anode and affecting the electrolysis efficiency.
  • the present invention provides a green and efficient refining method for complex crude tin.
  • the present invention adopts the following technical solution:
  • a green and efficient refining method for complex crude tin including the following steps:
  • the crude tin melt obtained by reduction smelting is subjected to two condensation iron removal and arsenic operations to make the iron content in the crude tin melt less than 0.01wt%, and the produced ethyl tin and condensation slag are Merge into the centrifuge for iron and arsenic removal operations, so that the tin content in the centrifugal slag is less than 50wt%;
  • step (3) Continuously crystallize the crude tin melt obtained in step (2) to remove lead, bismuth, and silver, and produce a refined tin product with a tin content greater than 99.90wt%, which meets the GB/T728-2020Sn99.90AA standard;
  • step (2) perform continuous crystallization to remove lead, bismuth, and silver from the crude tin melt obtained in step (2), so that the silver content in the crude tin melt is less than 0.0005wt%;
  • step (3) The crude tin melt obtained in step (3) is subjected to vacuum volatilization to deeply remove lead and bismuth, and a refined tin product with a tin content greater than 99.95wt% or 99.99wt% is produced, complying with GB/T728-2020Sn99.95AA or GB /T728—2020Sn99.99A standard.
  • the present invention provides a green and efficient refining process technology for complex crude tin, which can produce refined tin that meets the GB/T728-2020 grade standard by removing impurity elements in the crude tin.
  • the present invention provides a green and efficient method for refining complex crude tin.
  • crude tin materials containing impurities of different types and compositions produced during the smelting and secondary resource recovery processes "centrifugal condensation-directional oxidation-continuous crystallization-
  • the "vacuum volatilization” technology for purifying crude tin flexibly combines centrifugal condensation, directional oxidation, continuous crystallization, and vacuum volatilization to achieve the classification and step-by-step deep removal of impurities to produce refined tin products.
  • the highly impurity crude tin undergoes two condensation treatments, and then directional oxidation removes copper, lead, antimony, arsenic, and nickel, and then uses continuous crystallization to remove lead, bismuth, and silver to produce Sanjiu tin products. It also provides a continuous crystallization method to remove lead, bismuth, and silver before vacuuming. A method for deeply removing lead and bismuth through volatilization to produce high-purity tin and lead-bismuth alloy products with a purity of 395 or 49.
  • the key to the method provided by the invention is that the produced ethyl tin and condensation slag are combined and processed by a centrifuge, which reduces the amount of produced slag and the tin content in the slag.
  • a centrifuge which reduces the amount of produced slag and the tin content in the slag.
  • directional oxidation is used to remove copper, lead, antimony, arsenic and nickel, and the copper in the crude tin is accurately controlled.
  • the content of lead, antimony, arsenic and nickel reduces the amount of slag produced and the tin content in the slag.
  • the combination of continuous crystallization and vacuum evaporation can produce various grades of refined tin products. The entire process is safe and controllable, easy to operate, requires simple equipment, and has strong adaptability to raw materials.
  • Coarse tin with different tin compositions can be effectively processed. , the direct tin recovery rate is high, the amount of waste residue is small, and different processes can be selected to obtain refined tin that meets the standards of each grade of GB/T728-2020.
  • the key to the method provided by the present invention is that the produced ethyl tin and condensate slag are combined and enter a centrifuge to remove iron and arsenic, and only a slag with a tin content of less than 50% is produced.
  • Directed oxidation controls the content of copper, arsenic, nickel and antimony, so that the amount of slag in the process is greatly reduced, and the direct recovery rate of tin is improved.
  • the pyro-refining process of the prior art, as shown in FIG2, has a direct recovery rate of about 78% of tin. After the improved process, the direct recovery rate of tin reaches 86.5%, which has huge environmental benefits, economic benefits and safety benefits for tin production enterprises.
  • the ethyl tin and condensation slag produced by condensation in step (1) are combined into a centrifuge to remove iron and arsenic. Only one kind of slag with a tin content of less than 50% is produced. In the original process, there are two kinds of slag produced. The centrifugal slag is separated. and carbon residue.
  • Directional oxidation strictly controls the copper content in the crude tin melt to be less than 0.05%, the arsenic content is less than 0.2%, the nickel content is less than 0.005%, and the antimony content is less than 0.015%, reducing the output of process slag.
  • the crude tin melt obtained by reduction smelting is a crude tin melt with a tin content of >75wt% obtained by using existing reduction smelting technology.
  • the method for condensation iron and arsenic removal is as follows: use water spray or water jacket cooling to cool the crude tin melt obtained by reduction smelting to 220-240°C, add sawdust and stir thoroughly, stir The time is 1-2h, and the stirring speed is: 2/3 stirring time 528r/min low speed stirring, 1/3 stirring time 1057r/min high speed stirring, so that the condensed iron and arsenic are adsorbed on the sawdust to form a gray-white scum. , causing iron and arsenic to condense and precipitate from the crude tin melt.
  • the method for removing copper, arsenic, nickel and antimony by directional oxidation is: combining the crude tin melt produced by the second condensation operation in step (1) and the centrifuge iron and arsenic removal operation. Combine the crude tin melt and add sulfur for heating and stirring.
  • the mass ratio of copper content to sulfur in the crude tin melt is 3:1, the heating temperature is 220-260°C, the stirring time is 0.5-1h, and the stirring speed is: 2/ 3 Stirring time: 528r/min low-speed stirring, 1/3 stirring time: 1057r/min high-speed stirring to fully react with copper and sulfur to form gray-black scum and remove it; heat the crude tin melt to above 300°C, add aluminum particles,
  • the mass ratio of arsenic, nickel and aluminum particles in the crude tin melt is 2:1. Heat the crude tin melt to above 320°C and stir for 0.5-1h.
  • the stirring speed is: 2/3. Stirring time: 528r/min. Stir at low speed.
  • 1/3 stirring time 1057r/min high-speed stirring to fully react with arsenic and aluminum to form gray-black scum and remove it; heat the crude tin melt to above 300°C, add aluminum particles, the crude tin melt contains antimony and aluminum The mass ratio of the particles is 2:1. Cool the crude tin melt to 220-240°C and stir for 0.5-1h. The stirring speed is: 2/3 stirring time 528r/min low speed stirring, 1/3 stirring time 1057r/min high speed Stir to fully react with nickel, antimony and aluminum, and add ammonium chloride to form slag. Add 20kg of ammonium chloride for every 50 tons of crude tin melt to remove the gray-black scum formed by nickel, antimony and aluminum.
  • the method for continuously crystallizing lead, bismuth, and silver is as follows: putting the crude tin melt flow into the continuous crystallizer, spraying water to cool down, and condensing the crude tin melt into crystals, while using The spiral pushes the crystal to the fine tin end of the crystallizer.
  • the bottom of the tank of the crystallizer is heated with electricity.
  • the temperature is 500-600°C, so that the lead, bismuth and silver are enriched in the rough solder, and flow out as a liquid from the bottom of the crystallizer tank, thereby removing the lead, bismuth and silver.
  • the distillation treatment method is: put the crude tin melt into a vacuum furnace, control the pressure in the furnace to 1 ⁇ 100Pa, and the distillation temperature to 900 ⁇ 1300°C , volatilize and remove lead and bismuth.
  • Figure 1 is a process flow diagram of the method of the present invention
  • FIG2 is a flow chart of pyrometallurgy in the prior art
  • FIG. 3 is a flow chart showing the electrolytic refining principle of the prior art.
  • a green and efficient refining method for complex crude tin including the following steps:
  • the method of condensation and removal of iron and arsenic is as follows: the crude tin melt obtained by reduction smelting is cooled to 220°C by water spraying or water jacket cooling, sawdust is added and fully stirred for 1 hour, and the stirring speed is: 2/3 stirring time 528r/min low speed stirring, 1/3 stirring time 1057r/min high speed stirring, so that the condensed iron and arsenic are absorbed and attached to the sawdust to form grayish white scum, so that the iron and arsenic are condensed and precipitated from the crude tin melt;
  • the method for removing copper, arsenic, nickel and antimony by directional oxidation is: combine the crude tin melt produced by the second condensation operation in step (1) with the crude tin melt produced by the centrifuge removal of iron and arsenic and add sulfur Heating and stirring, the mass ratio of copper content and sulfur in the crude tin melt is 3:1, the heating temperature is 220°C, the stirring time is 0.5h, the stirring speed is: 2/3, the stirring time is 528r/min, low-speed stirring, 1/3 The stirring time is 1057r/min. Stir at high speed to fully react with copper and sulfur to form gray-black scum and remove it; heat the crude tin melt to 310°C and add aluminum particles.
  • the amount of arsenic, nickel and the mass of the aluminum particles in the crude tin melt The ratio is 2:1. Heat the crude tin melt to 330°C and stir for 0.5h. The stirring speed is: 2/3 stirring time 528r/min low speed stirring, 1/3 stirring time 1057r/min high speed stirring to make arsenic and aluminum React fully to form gray-black scum and remove it; heat the crude tin melt to 310°C, add aluminum particles, the mass ratio of antimony content in the crude tin melt to aluminum particles is 2:1, cool the crude tin melt to 220°C, stir for 0.5h, the stirring speed is: 2/3 stirring time 528r/min low speed stirring, 1/3 stirring time 1057r/min high speed stirring, so that nickel, antimony and aluminum can fully react, and ammonium chloride is added to create slagging. Add 20kg ammonium chloride to every 50 tons of crude tin melt to remove the gray-black scum formed by nickel, antimony and aluminum;
  • the copper content in the crude tin melt is 0.028wt%, the arsenic content is 0.176wt%, the nickel content is 0.0008wt%, and the antimony content is 0.0119wt%;
  • step (3) Continuously crystallize the crude tin melt obtained in step (2) to remove lead, bismuth and silver;
  • the method for continuous crystallization to remove lead, bismuth and silver is as follows: put the crude tin melt flow into the continuous crystallizer, spray water to cool down, so that the crude tin melt condenses into crystals, and at the same time, use a spiral to push the crystals to the fine center of the crystallizer.
  • the bottom of the crystallizer tank is heated with electricity at a heating temperature of 200°C, so that the lead, bismuth and silver are enriched in the rough solder, and flow out in a liquid form from the bottom of the crystallizer tank, thereby removing the lead, bismuth and silver.
  • a green and efficient refining method for complex crude tin including the following steps:
  • the method for condensation iron and arsenic removal is as follows: use water spray or water jacket cooling to cool the crude tin melt obtained by reduction smelting to 230°C, add sawdust and stir thoroughly, the stirring time is 1.5h, and the stirring speed is: 2/ 3 Stirring time: 528r/min low-speed stirring, 1/3 stirring time: 1057r/min high-speed stirring, so that the condensed iron and arsenic are adsorbed on the sawdust to form gray-white scum, and the iron and arsenic are condensed from the crude tin melt. precipitate;
  • the method for removing copper, arsenic, nickel and antimony by directional oxidation is: combine the crude tin melt produced by the second condensation operation in step (1) with the crude tin melt produced by the centrifuge removal of iron and arsenic and add sulfur Heating and stirring, the mass ratio of copper content and sulfur in the crude tin melt is 3:1, the heating temperature is 240°C, the stirring time is 0.7h, the stirring speed is: 2/3, the stirring time is 528r/min, low-speed stirring, 1/3 Stir at a high speed of 1057r/min to fully react with copper and sulfur to form gray-black scum and remove it; heat the crude tin melt to 320°C and add aluminum particles.
  • the crude tin melt contains arsenic, nickel, and the mass of the aluminum particles.
  • the ratio is 2:1.
  • the stirring speed is: 2/3 stirring time 528r/min low speed stirring, 1/3 stirring time 1057r/min high speed stirring to make arsenic and aluminum React fully to form gray-black scum and remove it; heat the crude tin melt to 320°C, add aluminum particles, the mass ratio of antimony content in the crude tin melt to aluminum particles is 2:1, cool the crude tin melt to 230°C, stir for 0.7h, the stirring speed is: 2/3 stirring time 528r/min low speed stirring, 1/3 stirring time 1057r/min high speed stirring, so that nickel, antimony and aluminum can fully react, and add Add ammonium chloride to make slag, add 20kg ammonium chloride for every 50 tons of crude tin melt, and remove the gray-black scum formed by nickel, antimony and aluminum;
  • the copper content in the crude tin melt is 0.034wt%, the arsenic content is 0.185wt%, the nickel content is 0.0007wt%, and the antimony content is 0.0093wt%;
  • step (3) Continuously crystallize the crude tin melt obtained in step (2) to remove lead, bismuth and silver;
  • the method for continuous crystallization to remove lead, bismuth and silver is as follows: put the crude tin melt flow into the continuous crystallizer, spray water to cool down, so that the crude tin melt condenses into crystals, and at the same time, use a spiral to push the crystals to the fine center of the crystallizer.
  • the bottom of the crystallizer tank is heated with electricity, and the heating temperature is 400°C, so that the lead, bismuth and silver are enriched in the rough solder, and flow out in a liquid form from the bottom of the crystallizer tank, thereby removing the lead, bismuth and silver;
  • the silver content in the crude tin melt is less than 0.0003wt%
  • the method of distillation treatment is as follows: put the crude tin melt into a vacuum furnace, control the pressure in the furnace to 2Pa, and the distillation temperature to 900°C to volatilize and remove lead and bismuth;
  • a green and efficient refining method for complex crude tin including the following steps:
  • the method for condensation iron and arsenic removal is as follows: use water spray or water jacket cooling to cool the crude tin melt obtained by reduction smelting to 240°C, add sawdust and stir thoroughly, the stirring time is 2h, and the stirring speed is: 2/3 The stirring time is 528r/min at low speed, and the 1/3 stirring time is 1057r/min at high speed to make the cold
  • the condensed iron and arsenic are adsorbed and adsorbed on the sawdust to form gray-white scum, causing the iron and arsenic to condense and precipitate from the crude tin melt;
  • the iron content in the crude tin melt is 0.0044wt%, and the produced ethyl tin and condensate slag are combined and put into a centrifuge for iron and arsenic removal, so that the tin content in the centrifugal slag is 48.58wt%;
  • the method for removing copper, arsenic, nickel and antimony by directional oxidation is: combine the crude tin melt produced by the second condensation operation in step (1) with the crude tin melt produced by the centrifuge removal of iron and arsenic and add sulfur Heat and stir.
  • the mass ratio of copper content and sulfur in the crude tin melt is 3:1.
  • the heating temperature is 260°C.
  • the stirring time is 1 hour.
  • the stirring speed is: 2/3.
  • the copper content in the crude tin melt is 0.037wt%, the arsenic content is 0.190wt%, the nickel content is 0.0007wt%, and the antimony content is 0.0105wt%;
  • step (3) subjecting the crude tin melt obtained in step (2) to continuous crystallization to remove lead, bismuth and silver;
  • the method for continuous crystallization to remove lead, bismuth and silver is as follows: put the crude tin melt flow into the continuous crystallizer, spray water to cool down, so that the crude tin melt condenses into crystals, and at the same time, use a spiral to push the crystals to the fine center of the crystallizer. tin During this process, the bottom of the crystallizer tank is heated with electricity, and the heating temperature is 600°C, so that the lead, bismuth and silver are enriched in the rough solder, and flow out in a liquid form from the bottom of the crystallizer tank, thereby removing the lead, bismuth and silver;
  • the method of distillation treatment is as follows: put the crude tin melt into a vacuum furnace, control the pressure in the furnace to 30Pa, and the distillation temperature to 1300°C to volatilize and remove lead and bismuth;
  • step (2) Add the crude tin obtained in step (1) into a centrifuge, raise the temperature to 510°C, and start the centrifuge to separate the liquid tin and slag in the centrifuge to produce iron-arsenic slag;
  • step (3) the crude tin A obtained in step (1) and the liquid crude tin obtained in step (2) are combined, and the crude tin A is cooled again to 230° C. by spraying water or cooling with a water jacket, and the stirrer is started, and sawdust is added and stirred thoroughly for 1.5 h.
  • the stirring speed is: 2/3 stirring time 528 r/min low speed stirring, 1/3 stirring time 1057 r/min high speed stirring, so that the condensed iron and arsenic are absorbed and attached to the sawdust, forming an off-white scum (i.e., carbon slag) for removal;
  • step (3) Add the crude tin obtained in step (3) to sulfur and heat and stir.
  • the mass ratio of copper amount in the crude tin melt to sulfur is 3:1, the heating temperature is 240°C, the stirring time is 0.8h, and the stirring speed is: 2/ 3 Stirring time: 528r/min at low speed, 1/3 stirring time: 1057r/min at high speed to fully react with copper and sulfur to form gray-black scum (i.e. sulfur slag) and remove it;
  • step (4) Put the coarse tin flow obtained in step (4) into the continuous crystallizer, spray water to cool down, and condense the crude tin melt into crystals. At the same time, use a spiral to push the crystals to the fine tin end of the crystallizer.
  • the bottom of the crystallizer tank is heated with electricity, and the heating temperature is 400°C, so that the lead, bismuth and silver are enriched in the rough solder, and flow out in a liquid form from the bottom of the crystallizer tank, thereby removing the lead, bismuth and silver;
  • the direct tin recovery rate of this process is 77.8%, and the slags produced include iron-arsenic slag, carbon slag, sulfur slag, and aluminum slag.
  • the direct recovery rate of tin in Example 1 reaches 87.1%
  • the direct recovery rate of tin in Example 2 reaches 86.7%
  • the direct recovery rate of tin in Example 3 reaches 86.5%.
  • the slags produced include iron-arsenic slag, sulfur slag, and aluminum slag, and no carbon slag is produced.
  • the output of the crystallizer is increased from the original 18-20 tons to more than 30 tons.

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Abstract

一种复杂粗锡绿色高效的精炼方法，属于有色金属火法冶炼技术领域，包括：将还原熔炼得到的粗锡熔体，进行两次凝析除铁、砷作业，将产出的乙锡和凝析渣合并进入离心机进行除铁、砷作业；将第二次凝析作业产出的粗锡熔体和离心机除铁、砷作业产出的粗锡熔体合并进行定向氧化除铜、砷、镍、锑；将处理所得粗锡熔体进行连续结晶除铅、铋、银；或，将处理所得粗锡熔体进行连续结晶除铅、铋、银；将处理所得粗锡熔体进行真空挥发深度除铅、铋。整个工艺过程安全可控，对原料普适性高，含锡成分不同的粗锡均能得到有效处理，锡直收率高，废渣产生量少，绿色环保，可选择不同的工艺得到符合GB/T728—2020各品级标准精锡。

Description

一种复杂粗锡绿色高效的精炼方法 技术领域
本发明属于有色金属火法冶炼技术领域，更具体的说是涉及一种复杂粗锡绿色高效的精炼方法。
背景技术
锡在人类文明进程中一直扮演着重要角色，是支撑军工、航空航天、电子信息、现代光伏等高科技产业和现代工业不可或缺的战略金属。我国锡储量、产量和消费量均居世界首位。2021年我国锡储量110万吨，约占全球锡储量23％；精锡产量16.52万吨，约占世界总产量44％，连续二十年居世界第一；精锡消费量18.37万吨，约占世界消费量47％。云南省是全球锡产业核心产区，云南个旧被誉为世界“锡都”，云南锡资源储量32万吨，居我国首位，约占世界总储量7％；精锡产量为13万吨，约占全国产量80％，占全球产量35％。
全球锡矿资源以脉锡矿为主，脉锡矿共伴生组分多，锡矿作为单一矿产形式出现的只占12％。共生及伴生的矿产通常含有铜、铅、锑、铋、银、铁、硫、砷等有价金属；高品质砂锡矿主要集中于东南亚地区，但也日渐枯竭。截至2021年底，全球锡资源总储量为490万吨，其中中国、印尼、缅甸、澳大利亚、巴西五个国家的储量约占全球73％。我国锡矿资源储量高度集中，云南、广西、湖南、广东、内蒙古等五个省区占全国储量的85％以上。
粗锡传统精炼技术中，(1)粗锡传统火法精炼技术，粗锡火法精炼工艺主要包含以下步骤：乙锡反射炉除铁、砷，甲锡熔析凝析除铁、砷，加硫除铜，结晶除铅、铋，加铝除砷、锑，最终产出精锡。火法精炼技术杂质脱除难度大、工艺流程长、锡直收率低、作业成本高，且影响产品质量，同时产 出大量难处理精炼废渣，存在严重的环境隐患、安全风险及职工职业健康危害等问题。
(2)粗锡电解精炼技术，粗锡电解精炼技术是利用金属锡与杂质元素标准电极电位差异，在一定温度和直流电流作用下，在特定溶液中使主体金属锡与其它杂质元素分离提纯。在电解过程中锡在阴极析出，比锡电位更正的金属(锑、铋、砷、铜、银等)残留在阳极泥中，再从阳极泥中综合回收。由于铅锡电位相近，通过湿法电解难以分离。湿法处理技术对粗锡原料的要求较高，杂质铜、铁含量均需小于1％，砷锑总含量需小于1％。该技术最早采用过盐酸电解液体系，但粗锡电解温度较高，盐酸易挥发形成酸雾，生产环境恶劣，对生产人员的身体健康造成极大危害；后转为使用硫酸电解液体系，但杂质铅电解后会与硫酸根离子结合生成硫酸铅，与其他不溶物粘附在阳极表面形成固体膜，使阳极钝化，影响电解效率；后来普遍采用硅氟酸电解液体系，但此方法主要用于焊锡等含锡双金属原料电解，目前粗锡电解直接生产精锡的工艺已经被淘汰。
随着国际形势复杂化与国内环保要求严格化，东南亚高品位砂锡矿供给不足，国内锡冶炼企业以低品位复杂锡矿为主要原料，导致冶炼出的粗锡纯度下降，杂质种类不断增多，成分日益复杂，铁、镍、砷、锑、铜等杂质含量显著增加；随着电子、光伏等现代产业的飞速发展，锡消费市场持续旺盛，产生大量含锡废料、电镀泥、波峰焊渣等含锡二次资源，从其中回收的粗锡，含大量的铜、镍、银、铋、铅等杂质，处理难度远大于原生矿产出的粗锡。
传统粗锡精炼技术杂质脱除难、工艺流程长、锡直收率低、作业成本高、环保压力大，严重制约了锡行业的高质量发展；与此同时，现代工业应用对精锡品质提出更高要求，锡锭标准日益苛刻，亟需对粗锡精炼技术进行升级，绿色短流程生产各品级精锡，保障我国现代高技术产业稳定健康发展。
因此如何研发一种复杂粗锡绿色高效的精炼方法是本领域技术人员亟需解决的技术问题。
发明内容
有鉴于此，本发明提供了一种复杂粗锡绿色高效的精炼方法。
为了实现上述目的，本发明采用如下技术方案：
一种复杂粗锡绿色高效的精炼方法，包括以下步骤：
(1)采用传统方法，将还原熔炼得到的粗锡熔体，进行两次凝析除铁、砷作业，使粗锡熔体中铁含量小于0.01wt％，将产出的乙锡和凝析渣合并进入离心机进行除铁、砷作业，使离心渣中锡含量小于50wt％；
(2)采用传统方法，将步骤(1)第二次凝析作业产出的粗锡熔体和离心机除铁、砷作业产出的粗锡熔体合并进行定向氧化除铜、砷、镍、锑，使粗锡熔体中铜含量小于0.05wt％，砷含量小于0.2wt％，镍含量小于0.005wt％，锑含量小于0.015wt％；
(3)将步骤(2)处理所得粗锡熔体进行连续结晶除铅、铋、银，产出锡含量大于99.90wt％的精锡产品，符合GB/T728—2020Sn99.90AA标准；
或，将步骤(2)处理所得粗锡熔体进行连续结晶除铅、铋、银，使粗锡熔体中银含量小于0.0005wt％；
(4)将步骤(3)处理所得粗锡熔体进行真空挥发深度除铅、铋，产出锡含量大于99.95wt％或99.99wt％的精锡产品，符合GB/T728—2020Sn99.95AA或GB/T728—2020Sn99.99A标准。
本发明的有益效果：
为解决复杂锡矿冶炼出的粗锡纯度下降，含锡二次资源回收的粗锡杂质种类不断增多，成分日益复杂，铁、镍、砷、锑、铜等杂质含量显著增加，传统粗锡精炼技术杂质脱除难、工艺流程长、锡直收率低、作业成本高、环 保压力大等问题，本发明提供了复杂粗锡绿色高效精炼工艺技术，通过对粗锡中杂质元素的去除生产符合GB/T728—2020品级标准精锡。
本发明提供一种复杂粗锡绿色高效精炼的方法，针对冶炼及二次资源回收过程中产出的含不同种类、不同成分杂质的粗锡物料，采用“离心凝析-定向氧化-连续结晶-真空挥发”提纯粗锡的技术，将离心凝析、定向氧化、连续结晶、真空挥发灵活组合，实现杂质的分类分步深度脱除，生产精锡产品。即高杂粗锡经过两次凝析处理，再定向氧化除铜铅锑砷镍，然后采用连续结晶除铅铋银，产出三九锡产品，同时提供了连续结晶除铅铋银后再真空挥发深度除铅铋，生产纯度为三九五或四九的高纯锡及铅铋合金产品的方法。本发明提供的方法关键在于产出的乙锡和凝析渣用离心机合并处理，降低了产出渣量和渣含锡，同时采用定向氧化除铜铅锑砷镍，精确控制粗锡中铜铅锑砷镍含量，减少产出渣量和渣含锡。连续结晶与真空挥发相结合，可以生产各品级的精锡产品，整个工艺过程安全可控，操作方便，所需设备简单，对原料适应性强，含锡成分不同的粗锡均能得到有效处理，锡直收率高，废渣产生量少，可选择不同的工艺得到符合GB/T728—2020各品级标准精锡。
本发明提供的方法关键在于产出的乙锡和凝析渣，合并进入离心机除铁砷，只产出一种锡含量小于50％的渣，定向氧化控制铜砷镍锑含量，使得过程渣量大幅下降，提高锡的直收率，现有技术的火法精炼流程，如图2所示，锡的直收率约为78％，改进后的流程，锡直收率达到86.5％，对锡生产企业有巨大的环保效益、经济效益、安全效益。
步骤(1)中凝析产出的乙锡和凝析渣，合并进入离心机除铁砷，只产出一种锡含量小于50％渣，原流程，产出的有两种渣，离心析渣和炭渣。
定向氧化严格控制粗锡熔体中铜含量小于0.05％，砷含量小于0.2％，镍含量小于0.005％，锑含量小于0.015％，减少过程渣的产出。
进一步，上述步骤(1)中，还原熔炼得到的粗锡熔体是采用现有还原熔炼技术所得含锡量＞75wt％的粗锡熔体。
进一步，上述步骤(1)中，凝析除铁、砷作业的方法为：采用喷水或水套降温将还原熔炼得到的粗锡熔体降温至220-240℃，加入锯末进行充分搅拌，搅拌时间为1-2h，搅拌转速为：2/3搅拌时间528r/min低速搅拌，1/3搅拌时间1057r/min高速搅拌，使冷凝析出铁、砷吸除附在锯末上，形成灰白色的浮渣，使铁、砷从粗锡熔体中冷凝析出。
进一步，上述步骤(2)中，定向氧化除铜、砷、镍、锑的方法为：将步骤(1)第二次凝析作业产出的粗锡熔体和离心机除铁、砷作业产出的粗锡熔体合并加入硫磺加热搅拌，粗锡熔体含铜量和硫磺的质量比为3:1，加热温度为220-260℃，搅拌时间为0.5-1h，搅拌转速为：2/3搅拌时间528r/min低速搅拌，1/3搅拌时间1057r/min高速搅拌，使铜与硫磺充分反应，形成灰黑色的浮渣除去；将粗锡熔体升温至300℃以上，加入铝粒，粗锡熔体含砷镍量和铝粒的质量比为2:1，将粗锡熔体升温至320℃以上，搅拌0.5-1h，搅拌转速为：2/3搅拌时间528r/min低速搅拌，1/3搅拌时间1057r/min高速搅拌，使砷与铝充分反应，形成灰黑色的浮渣除去；将粗锡熔体升温至300℃以上，加入铝粒，粗锡熔体含锑量和铝粒的质量比为2:1，将粗锡熔体降温至220-240℃，搅拌0.5-1h，搅拌转速为：2/3搅拌时间528r/min低速搅拌，1/3搅拌时间1057r/min高速搅拌，使镍、锑与铝充分反应，并加入氯化铵造渣，每50吨粗锡熔体加入20kg氯化铵，使镍、锑与铝形成灰黑色的浮渣除去。
进一步，上述步骤(3)中，连续结晶除铅、铋、银，的方法为：将粗锡熔体流放入连续结晶机内，喷水降温，使粗锡熔体冷凝成为晶体，同时用螺旋将晶体推向结晶机的精锡端，在此过程中结晶机槽底用电进行加热，加热 温度为500-600℃，使铅铋银富集在粗焊锡中，从结晶机槽底以液体方式流出，从而除去铅铋银。
进一步，上述步骤(4)中，真空挥发深度除铅、铋，蒸馏处理的方法为：将粗锡熔体放入真空炉内，控制炉内压力为1～100Pa，蒸馏温度为900～1300℃，使铅、铋挥发除去。
附图说明
图1为本发明方法工艺流程图；
图2为现有技术的火法精炼流程图；
图3为现有技术的电解精炼原则流程图。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
GB/T728—2020各品级标准精锡的化学成分如下表：
实施例1
复杂粗锡绿色高效的精炼方法，包括以下步骤：
(1)将50t采用现有还原熔炼技术所得含锡量＞75wt％的粗锡熔体(粗锡熔体各成分的含量Sn93.42wt％，Pb2.88wt％，Sb0.32wt％，Bi0.27wt％；As1.22wt％，Cu0.52wt％，Fe0.98wt％，Ni0.048wt％)，进行两次凝析除铁、砷作业；
凝析除铁、砷作业的方法为：采用喷水或水套降温将还原熔炼得到的粗锡熔体降温至220℃，加入锯末进行充分搅拌，搅拌时间为1h，搅拌转速为：2/3搅拌时间528r/min低速搅拌，1/3搅拌时间1057r/min高速搅拌，使冷凝析出铁、砷吸除附在锯末上，形成灰白色的浮渣，使铁、砷从粗锡熔体中冷凝析出；
使粗锡熔体中铁含量为0.0072wt％，将产出的乙锡和凝析渣合并进入离心机进行除铁、砷作业，使离心渣中锡含量49.27wt％；
(2)将步骤(1)第二次凝析作业产出的粗锡熔体和离心机除铁、砷作业产出的粗锡熔体合并进行定向氧化除铜、砷、镍、锑；
定向氧化除铜、砷、镍、锑的方法为：将步骤(1)第二次凝析作业产出的粗锡熔体和离心机除铁、砷作业产出的粗锡熔体合并加入硫磺加热搅拌，粗锡熔体含铜量和硫磺的质量比为3:1，加热温度为220℃，搅拌时间为0.5h，搅拌转速为：2/3搅拌时间528r/min低速搅拌，1/3搅拌时间1057r/min高速搅拌，使铜与硫磺充分反应，形成灰黑色的浮渣除去；将粗锡熔体升温至310℃，加入铝粒，粗锡熔体含砷镍量和铝粒的质量比为2:1，将粗锡熔体升温至330℃，搅拌0.5h，搅拌转速为：2/3搅拌时间528r/min低速搅拌，1/3搅拌时间1057r/min高速搅拌，使砷与铝充分反应，形成灰黑色的浮渣除去；将粗锡熔体升温至310℃，加入铝粒，粗锡熔体含锑量和铝粒的质量比为2:1，将粗锡熔体降温至220℃，搅拌0.5h，搅拌转速为：2/3搅拌时间528r/min低速搅拌，1/3搅拌时间1057r/min高速搅拌，使镍、锑与铝充分反应，并加入氯化铵造渣，每50吨粗锡熔体加入20kg氯化铵，使镍、锑与铝形成灰黑色的浮渣除去；
使粗锡熔体中铜含量为0.028wt％，砷含量为0.176wt％，镍含量为0.0008wt％，锑含量为0.0119wt％；
(3)将步骤(2)处理所得粗锡熔体进行连续结晶除铅、铋、银；
连续结晶除铅、铋、银，的方法为：将粗锡熔体流放入连续结晶机内，喷水降温，使粗锡熔体冷凝成为晶体，同时用螺旋将晶体推向结晶机的精锡端，在此过程中结晶机槽底用电进行加热，加热温度为200℃，使铅铋银富集在粗焊锡中，从结晶机槽底以液体方式流出，从而除去铅铋银。产出锡含量大于99.90wt％的精锡产品(精锡产品各成分的含量Sn99.94wt％，Pb0.008wt％，Bi0.012wt％，Ag0.0003wt％)，符合GB/T728—2020Sn99.90AA标准。
实施例2
复杂粗锡绿色高效的精炼方法，包括以下步骤：
(1)将50t采用现有还原熔炼技术所得含锡量＞75wt％的粗锡熔体(粗锡熔体各成分的含量Sn88.65wt％，Pb6.88wt％，Sb0.32wt％，Bi0.34wt％，As1.22wt％，Cu1.02wt％，Fe0.62wt％，Ni0.062wt％)，进行两次凝析除铁、砷作业；
凝析除铁、砷作业的方法为：采用喷水或水套降温将还原熔炼得到的粗锡熔体降温至230℃，加入锯末进行充分搅拌，搅拌时间为1.5h，搅拌转速为：2/3搅拌时间528r/min低速搅拌，1/3搅拌时间1057r/min高速搅拌，使冷凝析出铁、砷吸除附在锯末上，形成灰白色的浮渣，使铁、砷从粗锡熔体中冷凝析出；
使粗锡熔体中铁含量为0.0063wt％，将产出的乙锡和凝析渣合并进入离心机进行除铁、砷作业，使离心渣中锡含量为47.53wt％；
(2)将步骤(1)第二次凝析作业产出的粗锡熔体和离心机除铁、砷作业产出的粗锡熔体合并进行定向氧化除铜、砷、镍、锑；
定向氧化除铜、砷、镍、锑的方法为：将步骤(1)第二次凝析作业产出的粗锡熔体和离心机除铁、砷作业产出的粗锡熔体合并加入硫磺加热搅拌，粗锡熔体含铜量和硫磺的质量比为3:1，加热温度为240℃，搅拌时间为0.7h，搅拌转速为：2/3搅拌时间528r/min低速搅拌，1/3搅拌时间1057r/min高速搅拌，使铜与硫磺充分反应，形成灰黑色的浮渣除去；将粗锡熔体升温至320℃，加入铝粒，粗锡熔体含砷镍量和铝粒的质量比为2:1，将粗锡熔体升温至340℃，搅拌0.7h，搅拌转速为：2/3搅拌时间528r/min低速搅拌，1/3搅拌时间1057r/min高速搅拌，使砷与铝充分反应，形成灰黑色的浮渣除去；将粗锡熔体升温至320℃，加入铝粒，粗锡熔体含锑量和铝粒的质量比为2:1，将粗锡熔体降温至230℃，搅拌0.7h，搅拌转速为：2/3搅拌时间528r/min低速搅拌，1/3搅拌时间1057r/min高速搅拌，使镍、锑与铝充分反应，并加 入氯化铵造渣，每50吨粗锡熔体加入20kg氯化铵，使镍、锑与铝形成灰黑色的浮渣除去；
使粗锡熔体中铜含量为0.034wt％，砷含量为0.185wt％，镍含量为0.0007wt％，锑含量为0.0093wt％；
(3)将步骤(2)处理所得粗锡熔体进行连续结晶除铅、铋、银；
连续结晶除铅、铋、银，的方法为：将粗锡熔体流放入连续结晶机内，喷水降温，使粗锡熔体冷凝成为晶体，同时用螺旋将晶体推向结晶机的精锡端，在此过程中结晶机槽底用电进行加热，加热温度为400℃，使铅铋银富集在粗焊锡中，从结晶机槽底以液体方式流出，从而除去铅铋银；
使粗锡熔体中银含量小于0.0003wt％；
(4)将步骤(3)处理所得粗锡熔体进行真空挥发深度除铅、铋；
真空挥发深度除铅、铋，蒸馏处理的方法为：将粗锡熔体放入真空炉内，控制炉内压力为2Pa，蒸馏温度为900℃，使铅、铋挥发除去；
产出锡含量大于99.95wt％的精锡产品(精锡产品各成分的含量Sn99.97wt％，Pb0.0037wt％，Bi0.0011wt％，Ag0.0003wt％)，符合GB/T728—2020Sn99.95AA标准。
实施例3
复杂粗锡绿色高效的精炼方法，包括以下步骤：
(1)将50t采用现有还原熔炼技术所得含锡量＞75wt％的粗锡熔体(粗锡熔体各成分的含量Sn89.74wt％，Pb5.88wt％，Sb0.74wt％，Bi0.35wt％，As0.94wt％，Cu0.83wt％，Fe1.12wt％，Ni0.068wt％)，进行两次凝析除铁、砷作业；
凝析除铁、砷作业的方法为：采用喷水或水套降温将还原熔炼得到的粗锡熔体降温至240℃，加入锯末进行充分搅拌，搅拌时间为2h，搅拌转速为：2/3搅拌时间528r/min低速搅拌，1/3搅拌时间1057r/min高速搅拌，使冷 凝析出铁、砷吸除附在锯末上，形成灰白色的浮渣，使铁、砷从粗锡熔体中冷凝析出；
使粗锡熔体中铁含量为0.0044wt％，将产出的乙锡和凝析渣合并进入离心机进行除铁、砷作业，使离心渣中锡含量为48.58wt％；
(2)将步骤(1)第二次凝析作业产出的粗锡熔体和离心机除铁、砷作业产出的粗锡熔体合并进行定向氧化除铜、砷、镍、锑；
定向氧化除铜、砷、镍、锑的方法为：将步骤(1)第二次凝析作业产出的粗锡熔体和离心机除铁、砷作业产出的粗锡熔体合并加入硫磺加热搅拌，粗锡熔体含铜量和硫磺的质量比为3:1，加热温度为260℃，搅拌时间为1h，搅拌转速为：2/3搅拌时间528r/min低速搅拌，1/3搅拌时间1057r/min高速搅拌，使铜与硫磺充分反应，形成灰黑色的浮渣除去；将粗锡熔体升温至330℃，加入铝粒，粗锡熔体含砷镍量和铝粒的质量比为2:1，将粗锡熔体升温至350℃，搅拌1h，搅拌转速为：2/3搅拌时间528r/min低速搅拌，1/3搅拌时间1057r/min高速搅拌，使砷与铝充分反应，形成灰黑色的浮渣除去；将粗锡熔体升温至330℃，加入铝粒，粗锡熔体含锑量和铝粒的质量比为2:1，将粗锡熔体降温至240℃，搅拌1h，搅拌转速为：2/3搅拌时间528r/min低速搅拌，1/3搅拌时间1057r/min高速搅拌，使镍、锑与铝充分反应，并加入氯化铵造渣，每50吨粗锡熔体加入20kg氯化铵，使镍、锑与铝形成灰黑色的浮渣除去；
使粗锡熔体中铜含量为0.037wt％，砷含量为0.190wt％，镍含量为0.0007wt％，锑含量为0.0105wt％；
(3)将步骤(2)处理所得粗锡熔体进行连续结晶除铅、铋、银；
连续结晶除铅、铋、银，的方法为：将粗锡熔体流放入连续结晶机内，喷水降温，使粗锡熔体冷凝成为晶体，同时用螺旋将晶体推向结晶机的精锡 端，在此过程中结晶机槽底用电进行加热，加热温度为600℃，使铅铋银富集在粗焊锡中，从结晶机槽底以液体方式流出，从而除去铅铋银；
使粗锡熔体中银含量为0.0001wt％；
(4)将步骤(3)处理所得粗锡熔体进行真空挥发深度除铅、铋；
真空挥发深度除铅、铋，蒸馏处理的方法为：将粗锡熔体放入真空炉内，控制炉内压力为30Pa，蒸馏温度为1300℃，使铅、铋挥发除去；
产出锡含量大于99.99wt％的精锡产品(精锡产品各成分的含量Sn99.993％，Pb0.0015％，Bi0.0011％，Ag0.0001％)，符合GB/T728—2020Sn99.99A标准。
图2现有技术的火法精炼流程的实施案例：
(1)将30t采用现有还原熔炼技术所得含锡量＞75wt％的粗锡熔体(粗锡熔体各成分的含量Sn92.38wt％，Pb4.36wt％，Sb0.42wt％，Bi0.38wt％，As1.04wt％，Cu0.58wt％，Fe0.72wt％，Ni0.03wt％)，喷水降温至450℃，得到甲粗锡液体和浮在液体表面的乙粗锡；
(2)将步骤(1)得到乙粗锡加入到离心机内，升温到510℃，启动离心机，使离心机内的液体锡与渣分离，产出铁砷渣；
(3)将步骤(1)得到甲粗锡与步骤(2)得到的液体粗锡合并在一起，采用喷水或水套降温将甲粗锡再次降温到230℃，开动搅机，并加入锯末进行充分搅拌，时间为1.5h，搅拌转速为：2/3搅拌时间528r/min低速搅拌，1/3搅拌时间1057r/min高速搅拌，使冷凝析出铁、砷吸除附在锯末上，形成灰白色的浮渣(即炭渣)除去；
(4)将步骤(3)得到粗锡加入硫磺加热搅拌，粗锡熔体铜量和硫磺的质量比为3:1，加热温度为240℃，搅拌时间为0.8h，搅拌转速为：2/3搅拌时间528r/min低速搅拌，1/3搅拌时间1057r/min高速搅拌，使铜与硫磺充分反应，形成灰黑色的浮渣(即硫渣)除去；
(5)将步骤(4)得到粗锡流放入连续结晶机内，喷水降温，使粗锡熔体冷凝成为晶体，同时用螺旋将晶体推向结晶机的精锡端，在此过程中结晶机槽底用电进行加热，加热温度为400℃，使铅铋银富集在粗焊锡中，从结晶机槽底以液体方式流出，从而除去铅铋银；
(6)将步骤(5)得到精锡晶体升温至310℃，加入铝粒，粗锡熔体含砷镍量和铝粒的质量比为2:1，将粗锡熔体升温至330℃，搅拌0.7h，搅拌转速为：2/3搅拌时间528r/min低速搅拌，1/3搅拌时间1057r/min高速搅拌，使砷与铝充分反应，形成灰黑色的浮渣除去；将粗锡熔体升温至310℃，加入铝粒，粗锡熔体含锑量和铝粒的质量比为2:1，将粗锡熔体降温至230℃，搅拌0.7h，搅拌转速为：2/3搅拌时间528r/min低速搅拌，1/3搅拌时间1057r/min高速搅拌，使镍、锑与铝充分反应，并加入氯化铵造渣，每30吨粗锡熔体加入20kg氯化铵，使镍、锑与铝形成灰黑色的浮渣除去；
产出锡含量大于99.90wt％的精锡产品(精锡产品各成分的含量Sn99.97wt％，Pb0.0201wt％，Bi0.011wt％，Ag0.0003wt％)，符合GB/T728—2020Sn99.90A标准。
该过程的锡直收率为77.8％，产出的渣有铁砷渣、炭渣、硫渣、铝渣。
改进后的流程，实施例1锡直收率达到87.1％，实施例2锡直收率达到86.7％，实施例3锡直收率达到86.5％，产出的渣有铁砷渣、硫渣、铝渣，没有炭渣产出，结晶机的产量由原来的18-20吨，提高到30吨以上。
对所公开的实施例的说明，使本领域专业技术人员能够实现或使用本发明。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的，本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下，在其它实施例中实现。因此，本发明将不会被限制于本文所示的这些实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。

Claims (5)

  1. 一种复杂粗锡绿色高效的精炼方法，其特征在于，包括以下步骤：
    (1)采用传统方法，将还原熔炼得到的粗锡熔体，进行两次凝析除铁、砷作业，使粗锡熔体中铁含量小于0.01wt％，将产出的乙锡和凝析渣合并进入离心机进行除铁、砷作业，使离心渣中锡含量小于50wt％；
    (2)采用传统方法，将步骤(1)第二次凝析作业产出的粗锡熔体和离心机除铁、砷作业产出的粗锡熔体合并进行定向氧化除铜、砷、镍、锑，使粗锡熔体中铜含量小于0.05wt％，砷含量小于0.2wt％，镍含量小于0.005wt％，锑含量小于0.015wt％；
    (3)将步骤(2)处理所得粗锡熔体进行连续结晶除铅、铋、银，产出锡含量大于99.90wt％的精锡产品，符合GB/T728—2020Sn99.90AA标准；
    或，将步骤(2)处理所得粗锡熔体进行连续结晶除铅、铋、银，使粗锡熔体中银含量小于0.0005wt％；
    (4)将步骤(3)处理所得粗锡熔体进行真空挥发深度除铅、铋，产出锡含量大于99.95wt％或99.99wt％的精锡产品，符合GB/T728—2020Sn99.95AA或GB/T728—2020Sn99.99A标准；
    所述步骤(2)中，定向氧化除铜、砷、镍、锑的方法为：将步骤(1)第二次凝析作业产出的粗锡熔体和离心机除铁、砷作业产出的粗锡熔体合并加入硫磺加热搅拌，粗锡熔体含铜量和硫磺的质量比为3:1，加热温度为220-260℃，搅拌时间为0.5-1h，搅拌转速为：2/3搅拌时间528r/min低速搅拌，1/3搅拌时间1057r/min高速搅拌，使铜与硫磺充分反应，形成灰黑色的浮渣除去；将粗锡熔体升温至300℃以上，加入铝粒，粗锡熔体含砷镍量和铝粒的质量比为2:1，将粗锡熔体升温至320℃以上，搅拌0.5-1h，搅拌转速为：2/3搅拌时间 528r/min低速搅拌，1/3搅拌时间1057r/min高速搅拌，使砷与铝充分反应，形成灰黑色的浮渣除去；将粗锡熔体升温至300℃以上，加入铝粒，粗锡熔体含锑量和铝粒的质量比为2:1，将粗锡熔体降温至220-240℃，搅拌0.5-1h，搅拌转速为：2/3搅拌时间528r/min低速搅拌，1/3搅拌时间1057r/min高速搅拌，使镍、锑与铝充分反应，并加入氯化铵造渣，每50吨粗锡熔体加入20kg氯化铵，使镍、锑与铝形成灰黑色的浮渣除去。
  2. 根据权利要求1所述的一种复杂粗锡绿色高效的精炼方法，其特征在于，所述步骤(1)中，还原熔炼得到的粗锡熔体是采用现有还原熔炼技术所得含锡量＞75wt％的粗锡熔体。
  3. 根据权利要求1所述的一种复杂粗锡绿色高效的精炼方法，其特征在于，所述步骤(1)中，凝析除铁、砷作业的方法为：采用喷水或水套降温将还原熔炼得到的粗锡熔体降温至220-240℃，加入锯末进行充分搅拌，搅拌时间为1-2h，搅拌转速为：2/3搅拌时间528r/min低速搅拌，1/3搅拌时间1057r/min高速搅拌，使冷凝析出铁、砷吸除附在锯末上，形成灰白色的浮渣，使铁、砷从粗锡熔体中冷凝析出。
  4. 根据权利要求1所述的一种复杂粗锡绿色高效的精炼方法，其特征在于，所述步骤(3)中，连续结晶除铅、铋、银，的方法为：将粗锡熔体流放入连续结晶机内，喷水降温，使粗锡熔体冷凝成为晶体，同时用螺旋将晶体推向结晶机的精锡端，在此过程中结晶机槽底用电进行加热，加热温度为500-600℃，使铅铋银富集在粗焊锡中，从结晶机槽底以液体方式流出，从而除去铅铋银。
  5. 根据权利要求1所述的一种复杂粗锡绿色高效的精炼方法，其特征在于，所述步骤(4)中，真空挥发深度除铅、铋，蒸馏处理的方法为：将粗锡熔体放 入真空炉内，控制炉内压力为1～100Pa，蒸馏温度为900～1300℃，使铅、铋挥发除去。
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