A method for synergistically and efficiently smelting tin-lead-containing materials
Patent Information
- Application Number
- CN202610904161.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-06-23
- Publication Date
- 2026-10-13
AI Technical Summary
但是该方法仍然存在工艺流程复杂、操作控制精度高、熔剂及还原剂消耗量大、能耗高等缺点
本发明既实现了多源含锡物料与含铅物料之间的协同熔炼，又实现了交互反应、还原反应、真空蒸馏三大核心技术之间的协同熔炼，能够解决现有混合熔炼工艺流程长、回收率低、污染大、能耗高、原料适应性小、环保压力大的缺点等问题，具备原料适应性强、流程短、锡铅回收率高等优点，能够实现复杂多源含锡、铅物料的高效、绿色综合回收利用。具体地：
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Figure CN122898754A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to a method for the co-efficiency smelting of tin-lead materials, belonging to the field of metal solid waste recycling technology. Background Technology
[0002] Tin and lead are both essential non-ferrous metals for the national economy. Tin is a strategic metal supporting the modern electronics and new energy industries, while lead is a core material for energy storage and radiation protection. The two can form high-performance tin-lead alloys for synergistic applications, covering dozens of industrial sectors including electronics, new energy, metallurgy, chemicals, medical, and military.
[0003] Tin is a strategic metal that is non-toxic, highly ductile, has excellent electrical conductivity, and is corrosion-resistant. Global tin consumption has shifted from traditional packaging to electronics and new energy sectors. In 2025, solder accounted for 48%–53% of global tin consumption, tin chemicals 16%, tinplate (tinplate) 11%, lead-acid batteries 7%, copper-tin alloys 5%–7%, and the remainder in emerging fields. With the trend towards lead-free production, tin has become the absolute core matrix material for electronic solder, accounting for half of global tin consumption. China's share of electronic solder consumption is even higher at 67%, earning it the title of the "industrial blood vessels" of the modern electronics industry. To date, there is no complete substitute in the field of microelectronic connections. Tinplate is a composite material made by plating tin onto the surface of cold-rolled thin steel sheets. Due to the non-toxic, corrosion-resistant, weldable, and glossy properties of the tin layer, it is a core material for food contact packaging and a traditional core consumption area for tin. Tin chemical products are divided into two main categories: organic tin and inorganic tin, accounting for about 16% of global tin consumption, and are widely used in building materials, chemicals, electroplating, agriculture, and other fields.
[0004] Lead is a high-density, corrosion-resistant, low-melting-point non-ferrous metal with excellent radiation shielding properties. Global lead consumption is highly concentrated, with over 80% of lead used in lead-acid battery manufacturing. The remaining applications are concentrated in radiation protection, chemical, metallurgical, and industrial manufacturing fields. Lead also boasts one of the most comprehensive recycling systems among non-ferrous metals globally, with recycled lead accounting for over 50% of global lead production, and over 60% in China. Lead-acid batteries, with their mature technology, low cost, high safety, stable charge / discharge performance, and well-established recycling system, are the most widely used secondary batteries globally and the absolute core of lead consumption, consistently accounting for over 80%. Lead's high atomic number and density give it extremely strong radiation attenuation and shielding capabilities, making it an irreplaceable radiation protection material in the medical and nuclear industries.
[0005] Generally, tin-containing materials, such as lead pyrometallurgical refining processes, produce oxide slag containing 30-50% tin and 10-30% lead. For example, in patent application number 2020100567563, a tin-containing material recycling and smelting process involves ball milling the tin-containing material, mixing it with soda ash and a reducing agent to form granules, and then smelting it to obtain a tin alloy. The tin alloy is then separated under vacuum to obtain refined tin. However, this method still has disadvantages such as complex process flow, high operational control precision, large consumption of flux and reducing agent, and high energy consumption. Summary of the Invention
[0006] To address the problems and shortcomings of existing technologies, this invention provides a method for the synergistic and efficient smelting of tin- and lead-containing materials. This invention synergistically smelts tin- and lead-containing materials from multiple sources, achieving synergistic smelting among three core technologies: interactive reaction, reduction reaction, and vacuum distillation. This avoids the drawbacks of traditional processes, such as long flow rates, low recovery rates, high pollution, high energy consumption, limited raw material adaptability, and significant environmental impact. This technology achieves tin and lead recovery rates of over 98%, representing a highly efficient and clean short-process technology for the comprehensive recovery of tin- and lead-containing materials. This invention is achieved through the following technical solutions.
[0007] A method for efficient smelting of tin-lead containing materials, the specific steps of which are as follows: Step 1: Mix the tin-containing material with SnO2 as the main tin phase and the lead-containing material with PbS and PbSO4 as the main lead phase evenly to obtain a homogeneous material. Step 2: Heat the mixed materials to melt them. The materials quickly melt and react with each other to achieve synergistic melting, producing tin-lead alloy and slag. Step 3: Add a reducing agent to the slag and blow in oxygen-enriched air for strong reduction smelting to obtain secondary lead-tin alloy and secondary slag. Step 4: The tin-lead alloy obtained in Step 2 and the secondary lead-tin alloy obtained in Step 3 are separated by continuous vacuum distillation to produce crude tin and crude lead, which are then sent to the refining process.
[0008] The tin-containing material in step 1 is tin recycling waste or low-grade tin concentrate. Tin recycling waste includes, but is not limited to, tin slag, tin fumes, and tin particles.
[0009] In step 1, the lead-containing material is lead recycling waste or low-grade lead concentrate. Lead recycling waste includes, but is not limited to, lead-containing waste from the dismantling of waste lead-acid batteries, lead slag produced in the hydrometallurgical zinc smelting process, and lead fumes.
[0010] In step 1, the tin-containing materials and lead-containing materials are mixed evenly according to the mass ratio of SnO2 to PbO and PbSO4 of 1:1 to 3.
[0011] In step 2, the heating temperature is 1500~1700℃, the heating time should be controlled within 30~90min, and the alternating melting reaction time should be controlled within 30-120min.
[0012] In step 3, the reducing agent is pulverized coal or coke, and the amount of reducing agent added is 10-30% of the slag mass.
[0013] In step 3, the oxygen volume concentration in the oxygen-enriched air is 30%~70%, and the oxygen-enriched air flow rate is 30~100 m³ / h.
[0014] In step 4, the vacuum distillation is controlled at a vacuum level of 1~20Pa and a distillation temperature of 1050~1300℃, with segmented temperature control and graded condensation at 500~700℃.
[0015] In the tin-lead alloy obtained in step 2 and the secondary lead-tin alloy obtained in step 3, Sn+Pb≥95%.
[0016] The secondary slag obtained in step 2 above contains 0.5-3% Sn and <0.5% Pb, and is sent to the flue gasification process.
[0017] The synergistic smelting of tin-lead materials proposed in this invention mainly utilizes the core principle of the interactive reaction between SnO2 and PbS and PbSO4, as follows:
[0018] The residual tin and lead in the slag during the co-smelting process are further recovered using enhanced reduction technology, resulting in Sn (0.5~3%) and Pb <0.5% in the slag. The core principle is as follows:
[0019] The tin-lead alloy produced by the co-melting and enhanced reduction process of this invention uses a multi-stage continuous vacuum distillation technology to separate tin and lead. This technology utilizes the significant difference between the saturated vapor pressure and boiling point of tin and lead under low pressure. By controlling the distillation temperature and vacuum, lead is preferentially vaporized and escaped from the alloy melt, and is then directionally recovered by a condensation system to obtain crude lead. The non-volatile component tin remains in the liquid phase, achieving efficient separation and deep purification of the two components. This is the mainstream core technology for the current processing of tin-lead alloys.
[0020] The beneficial effects of this invention are: This invention achieves synergistic smelting of tin- and lead-containing materials from multiple sources, as well as synergistic smelting of three core technologies: interactive reaction, reduction reaction, and vacuum distillation. It addresses the shortcomings of existing mixed smelting processes, such as long flow rates, low recovery rates, high pollution, high energy consumption, limited raw material adaptability, and significant environmental impact. It boasts advantages such as strong raw material adaptability, short process flow, and high tin-lead recovery rates, enabling efficient and green comprehensive recycling of complex, multi-source tin- and lead-containing materials. Specifically: 1. This invention combines interactive reaction, reduction reaction, and vacuum distillation methods. Among them, the synergistic melting fully utilizes the interactive reaction principle of SnO2 with PbO and PbSO4, which has the advantages of fast melting speed and high thermal efficiency, realizing rapid melting of materials and full reaction, laying the foundation for large-scale processing. Moreover, the reaction process does not use any flux or auxiliary materials, which effectively reduces the operating cost of this technology and improves its economic benefits. 2. Enhanced reduction boasts advantages such as high reduction efficiency and strong adaptability. It can solve the problems of low valuable metal recovery rate and potential uneven melt mass transfer in the previous step. It can further adapt to changes in raw materials, forming continuous enhancement, thus enabling it to process low-grade, complex primary ores and widely sourced secondary materials that are difficult to handle with traditional processes. 3. By introducing multi-stage continuous vacuum distillation technology, this invention achieves efficient and green separation of tin-lead alloys, fully ensuring the quality of the final product. Attached Figure Description
[0021] Figure 1 This is a schematic diagram of the process of this invention. Detailed Implementation
[0022] The present invention will be further described below with reference to the accompanying drawings and specific embodiments. Example 1
[0023] like Figure 1 As shown, the specific steps of this synergistic and efficient smelting method for tin-lead materials are as follows: Step 1: Mix the tin-containing material (which is mainly SnO2 and refers to conventional tin dross) and the lead-containing material (which is mainly PbS and PbSO4 and refers to lead-containing waste from the dismantling of conventional waste lead-acid batteries) with the tin-containing material and the lead-containing material at a mass ratio of 1:2 to obtain a homogeneous mixture. Step 2: Heat the mixed materials to 1500℃ and melt them. The heating time should be controlled within 30 minutes. The rapid melting and interactive reaction of the materials should be controlled within 60 minutes to generate tin-lead alloy and slag. Step 3: Add a reducing agent (pulverized coal, added at 10% of the slag mass) to the slag, and blow in oxygen-enriched air (oxygen volume concentration in the oxygen-enriched air is 30%, and the flow rate of the oxygen-enriched air is 100 m³ / h) to carry out strong reduction smelting to obtain secondary lead-tin alloy and secondary slag. Step 4: The tin-lead alloy obtained in Step 2 and the secondary lead-tin alloy obtained in Step 3 are separated by continuous vacuum distillation. The vacuum distillation is controlled at a vacuum degree of 10 Pa and a distillation temperature of 1050℃, with staged temperature control and condensation from 500℃ to 700℃. The resulting crude tin and crude lead are sent to the refining process.
[0024] The tin-lead alloy obtained in step 2 and the secondary lead-tin alloy obtained in step 3 both contain Sn+Pb ≥ 95%; the secondary slag obtained in step 2 contains Sn 1% and Pb < 0.5%, and is sent to the fuming process. In this embodiment, the mass percentage of Sn in the crude tin is 95%, and the mass percentage of lead in the crude lead is 96%. Example 2
[0025] like Figure 1 As shown, the specific steps of this synergistic and efficient smelting method for tin-lead materials are as follows: Step 1: Mix the tin-containing material with SnO2 as the main tin phase (tin-containing material refers to conventional tin fumes) and the lead-containing material with PbS and PbSO4 as the main lead phase (lead-containing material refers to conventional lead slag produced in the wet zinc smelting process) evenly according to the mass ratio of SnO2 to PbO and PbSO4 of 1:2. Step 2: Heat the mixed materials to 1700℃ and melt them. The heating time should be controlled within 60 minutes. The rapid melting and interactive reaction of the materials should be controlled within 120 minutes to generate tin-lead alloy and slag. Step 3: Add a reducing agent (pulverized coal, the amount added is 30% of the slag mass) to the slag, and blow in oxygen-enriched air (the oxygen volume concentration in the oxygen-enriched air is 70%, and the flow rate of the oxygen-enriched air is 30 m³ / h) to carry out strong reduction smelting to obtain secondary lead-tin alloy and secondary slag. Step 4: The tin-lead alloy obtained in Step 2 and the secondary lead-tin alloy obtained in Step 3 are separated by continuous vacuum distillation. The vacuum distillation is controlled at a vacuum degree of 10 Pa and a distillation temperature of 1300℃, with staged temperature control and condensation from 500℃ to 700℃. The resulting crude tin and crude lead are sent to the refining process.
[0026] The tin-lead alloy obtained in step 2 and the secondary lead-tin alloy obtained in step 3 both contain Sn+Pb ≥ 95%; the secondary slag obtained in step 2 contains Sn 3% and Pb < 0.5%, and is sent to the fuming process. In this embodiment, the mass percentage of Sn in the crude tin is 95%, and the mass percentage of lead in the crude lead is 98%. Example 3
[0027] like Figure 1 As shown, the specific steps of this synergistic and efficient smelting method for tin-lead materials are as follows: Step 1: Mix the tin-containing material with SnO2 as the main tin phase (the tin-containing material is conventional tin slag, tin fume, tin particles and low-grade tin concentrate with a mass ratio of 1:1:1) and the lead-containing material with PbS and PbSO4 as the main lead phase (the lead-containing material refers to conventional waste lead-acid battery dismantling waste, lead slag, lead fume and low-grade lead concentrate produced in the hydrometallurgical zinc smelting process with a mass ratio of 1:1:1) evenly to obtain a homogeneous material. Step 2: Heat the mixed materials to 1600℃ and melt them. The heating time should be controlled within 40 minutes. The rapid melting and interactive reaction of the materials should be controlled within 100 minutes to produce tin-lead alloy and slag. Step 3: Add a reducing agent (pulverized coal, the amount added is 20% of the slag mass) to the slag, and blow in oxygen-enriched air (the oxygen volume concentration in the oxygen-enriched air is 50%, and the flow rate of the oxygen-enriched air is 50 m³ / h) to carry out strong reduction smelting to obtain secondary lead-tin alloy and secondary slag. Step 4: The tin-lead alloy obtained in Step 2 and the secondary lead-tin alloy obtained in Step 3 are separated by continuous vacuum distillation. The vacuum distillation is controlled at a vacuum degree of 10 Pa and a distillation temperature of 1200℃, with staged temperature control and condensation from 500 to 700℃. The resulting crude tin and crude lead are sent to the refining process.
[0028] The tin-lead alloy obtained in step 2 and the secondary lead-tin alloy obtained in step 3 both contain Sn+Pb≥95%; the secondary slag obtained in step 2 contains Sn3% and Pb<0.5%, and is sent to the fuming process. In this embodiment, the mass percentage of Sn in the crude tin is 90%, and the mass percentage of lead in the crude lead is 94%.
[0029] The specific embodiments of the present invention have been described in detail above with reference to the accompanying drawings. However, the present invention is not limited to the above embodiments. Within the scope of knowledge possessed by those skilled in the art, various changes can be made without departing from the spirit of the present invention.
Claims
1. A method for the efficient smelting of tin-lead containing materials, characterized in that... The specific steps are as follows: Step 1: Mix the tin-containing material with SnO2 as the main tin phase and the lead-containing material with PbS and PbSO4 as the main lead phase evenly to obtain a homogeneous material. Step 2: Heat the mixed materials and melt them to produce tin-lead alloy and slag; Step 3: Add a reducing agent to the slag and blow in oxygen-enriched air for strong reduction smelting to obtain secondary lead-tin alloy and secondary slag. Step 4: The tin-lead alloy obtained in Step 2 and the secondary lead-tin alloy obtained in Step 3 are separated by continuous vacuum distillation to produce crude tin and crude lead, which are then sent to the refining process.
2. The method for efficient smelting of tin-lead materials according to claim 1, characterized in that: The tin-containing material in step 1 is tin recycling waste or low-grade tin concentrate. Tin recycling waste includes, but is not limited to, tin slag, tin fumes, and tin particles.
3. The method for efficient smelting of tin-lead containing materials according to claim 1, characterized in that: In step 1, the lead-containing material is lead recycling waste or low-grade lead concentrate. Lead recycling waste includes, but is not limited to, lead-containing waste from the dismantling of waste lead-acid batteries, lead slag produced in the hydrometallurgical zinc smelting process, and lead fumes.
4. The method for efficient smelting of tin-lead containing materials according to claim 1, characterized in that: In step 1, the tin-containing materials and lead-containing materials are mixed evenly according to the mass ratio of SnO2 to PbO and PbSO4 of 1:1 to 3.
5. The method for efficient smelting of tin-lead containing materials according to claim 1, characterized in that: In step 2, the heating temperature is 1500~1700℃, the heating time should be controlled within 30~90min, and the alternating melting reaction time should be controlled within 30-120min.
6. The method for efficient smelting of tin-lead containing materials according to claim 1, characterized in that: In step 3, the reducing agent is pulverized coal or coke, and the amount of reducing agent added is 10-30% of the slag mass.
7. The method for efficient smelting of tin-lead containing materials according to claim 1, characterized in that: In step 3, the oxygen volume concentration in the oxygen-enriched air is 30%~70%, and the oxygen-enriched air flow rate is 30~100 m³ / h.
8. The method for efficient smelting of tin-lead containing materials according to claim 1, characterized in that: In step 4, the vacuum distillation is controlled at a vacuum level of 1~20Pa and a distillation temperature of 1050~1300℃, with segmented temperature control and graded condensation at 500~700℃.