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CN119120903A - A tin smelting method based on recycling of metallurgical waste slag - Google Patents

A tin smelting method based on recycling of metallurgical waste slag Download PDF

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Publication number
CN119120903A
CN119120903A CN202411199361.3A CN202411199361A CN119120903A CN 119120903 A CN119120903 A CN 119120903A CN 202411199361 A CN202411199361 A CN 202411199361A CN 119120903 A CN119120903 A CN 119120903A
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China
Prior art keywords
smelting
tin
recycling
waste slag
method based
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CN202411199361.3A
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Chinese (zh)
Inventor
韦明磊
蒋光佑
何鑫
陈登勇
刘瑞年
林成旭
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Liuzhou China Tin Colored And Design Institute Co ltd
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Liuzhou China Tin Colored And Design Institute Co ltd
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Priority to CN202411199361.3A priority Critical patent/CN119120903A/en
Publication of CN119120903A publication Critical patent/CN119120903A/en
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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
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/001—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
    • C22B25/00—Obtaining tin
    • C22B25/02—Obtaining tin 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
    • C22B25/00—Obtaining tin
    • C22B25/06—Obtaining tin from scrap, especially tin 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
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • C22B5/10—Dry methods smelting of sulfides or formation of mattes by solid carbonaceous reducing agents
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

The invention discloses a tin smelting method based on recycling of metallurgical waste residues, which comprises the following steps of 1) crushing and mixing tin-containing waste residues and a solvent, putting the crushed and mixed tin-containing waste residues and the solvent into a smelting furnace, introducing gas into the smelting furnace for oxygen-enriched smelting to generate smelting flue gas, wherein the solvent is a mixture of limestone and fluorite, the temperature of the smelting furnace is 1200-1300 ℃, the oxygen content of the gas is more than or equal to 50%, 2) adding a reducing agent into a solution obtained by smelting to mix and carry out reduction smelting, the reducing agent is coke, charcoal or coal dust, the reduction smelting temperature is 1100-1300 ℃, 3) adding a vulcanizing agent into the solution obtained by reduction smelting to mix and carry out vulcanization volatilization, and 4) recycling tin from the vulcanized and volatilized gas through a condensing, electric furnace smelting or absorption tower. The invention can improve the extraction rate of tin and has lower energy consumption.

Description

Tin smelting method based on recycling of metallurgical waste residues
Technical Field
The invention relates to the technical field of smelting, in particular to a tin smelting method based on recycling of metallurgical waste residues.
Background
Tin has good plasticity, corrosion resistance and conductivity, and is widely applied to industries of electronics, information, electrical appliances, chemical industry, metallurgy, building materials, machinery, food packaging and the like. Tin is usually contained in waste slag generated by smelting, and the waste slag is directly discarded to cause great waste, so that the extraction of tin from the waste slag is an effective tin recovery way, and the current tin extraction method has low extraction rate and high energy consumption and needs improvement.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a tin smelting method based on recycling of metallurgical waste residues, which can improve the tin extraction rate and has low energy consumption.
The technical scheme adopted by the invention is that the tin smelting method based on recycling of metallurgical waste residues comprises the following steps:
1) Crushing and mixing tin-containing waste residues and a solvent, putting the crushed and mixed solvent into a smelting furnace, introducing gas for oxygen-enriched smelting to generate smelting flue gas, wherein the solvent is a mixture of limestone and fluorite, the temperature of the smelting furnace is 1200-1300 ℃, and the oxygen content in the gas is more than or equal to 50%;
2) Adding a reducing agent into the solution obtained by smelting, and mixing to perform reduction smelting, wherein the reducing agent is coke, charcoal or coal dust, and the reduction smelting temperature is 1100-1300 ℃;
3) Adding a vulcanizing agent into the solution obtained by reduction smelting, and mixing for vulcanization and volatilization;
4) The gas evaporated by sulfuration is used for recovering tin through a condensing, electric furnace smelting or absorption tower.
As the preferable choice of the technical proposal, the grain diameter of the tin-containing waste residue and the crushed solvent is 1 cm to 3cm.
As the optimization of the technical scheme, the mass of the flux is 10-15% of the mass of the tin-containing waste residue.
As the optimization of the technical scheme, the mass ratio of the limestone to the fluorite is (5-3) (2-1).
As the optimization of the technical scheme, the smelting flue gas is filtered and then reacts with oxygen and sodium hydroxide to generate sodium sulfate, and the sodium sulfate is added into the vulcanization step.
As a preference of the technical scheme, the vulcanization temperature is 1000-1300 ℃.
As the optimization of the technical scheme, the vulcanizing agent is at least one of pyrite, pyrite and tin sulfide ore, and gypsum is added into the vulcanizing agent as an auxiliary vulcanizing agent.
As the preferable choice of the technical proposal, the added reducing agent is 15-35% of the mass of the solution.
Compared with the prior art, the invention has the following advantages:
1. The invention adopts oxygen-enriched smelting, improves the pressure and diffusion speed of oxygen in the furnace, improves the temperature and speed of fuel combustion, accelerates the melting of furnace burden and improves smelting efficiency.
2. The invention adopts the solvent with proper proportion, is beneficial to smelting and slagging effects and reduces the consumed energy.
3. The reducing agent and the vulcanizing agent adopted by the invention improve the reducing and vulcanizing effects and the extraction rate.
4. According to the invention, the generated smoke is used for preparing the substance with the vulcanizing effect, so that the vulcanizing effect is improved, the smoke can be effectively treated, and the energy consumption for treating the smoke is reduced.
Detailed Description
The present invention will be described in detail with reference to specific examples.
The following examples adopt the same tin-containing waste slag to smelt under different conditions, and the elements in the tin-containing waste slag comprise the following components:
pb1.35%, sn2.56%, feO23.46%, al 2O33.11％,SiO2 5.31.31%, zn2.56%, caO7.34%, and others.
The embodiment 1 is a tin smelting method based on recycling of metallurgical waste residues, comprising the following steps:
1) Crushing tin-containing waste residues and a solvent, mixing, placing the crushed tin-containing waste residues and the crushed solvent into a smelting furnace, introducing gas to perform oxygen-enriched smelting to generate smelting flue gas, wherein the particle size of the crushed tin-containing waste residues and the crushed solvent is 1cm, the solvent is a mixture of limestone and fluorite, the mass ratio of the limestone to the fluorite is 5:2, the mass of the flux is 15% of the mass of the tin-containing waste residues, the temperature of the smelting furnace is 1200 ℃, and the oxygen content in the gas is 70%;
2) Adding a reducing agent into the solution obtained by smelting, mixing, and carrying out reduction smelting, wherein the reducing agent is coke, the reduction smelting temperature is 1300 ℃, and the added reducing agent is 35% of the mass of the solution.
3) Adding a vulcanizing agent into the solution obtained by reduction smelting for vulcanization volatilization, wherein the vulcanization temperature is 1200 ℃, the vulcanizing agent is pyrite, the vulcanizing agent is 10% of the mass of the solution, gypsum is added into the vulcanizing agent as an auxiliary vulcanizing agent, the mass of the gypsum is 5% of the mass of the vulcanizing agent, the smelting flue gas is filtered and then reacts with oxygen and sodium hydroxide to generate sodium sulfate, and the sodium sulfate is added into the vulcanization step.
4) The gas evaporated by sulfuration is used for recovering tin through an absorption tower, a chemical solvent is used for spraying and absorbing tin compounds in the absorption tower, and then metal tin is reduced through chemical reaction.
In the final slag of this example, the tin content was reduced from Sn2.56% to Sn0.45%.
Example 2 tin smelting method based on metallurgical waste residue reuse, comprising the following steps:
1) Crushing tin-containing waste residues and a solvent, mixing, placing the crushed tin-containing waste residues and the crushed solvent into a smelting furnace, introducing gas to perform oxygen-enriched smelting to generate smelting flue gas, wherein the particle size of the crushed tin-containing waste residues and the crushed solvent is 3cm, the solvent is a mixture of limestone and fluorite, the mass ratio of the limestone to the fluorite is 3:1, the mass of the flux is 10% of the mass of the tin-containing waste residues, the temperature of the smelting furnace is 1300 ℃, and the oxygen content in the gas is 85%;
2) Adding a reducing agent into the solution obtained by smelting, mixing, and carrying out reduction smelting, wherein the reducing agent is coal powder, the reduction smelting temperature is 1100 ℃, and the added reducing agent is 15% of the mass of the solution.
3) Adding a vulcanizing agent into the solution obtained by reduction smelting for vulcanization volatilization, wherein the vulcanization temperature is 1300 ℃, the vulcanizing agent is mixed by pyrite and thiotin ore, the mass ratio of the pyrite to the thiotin ore is 3:1, gypsum is added into the vulcanizing agent as an auxiliary vulcanizing agent, the mass of the gypsum is 10% of the mass of the vulcanizing agent, the smelting flue gas is filtered and then reacts with oxygen and sodium hydroxide to generate sodium sulfate, and the sodium sulfate is added into the vulcanization step.
4) And (3) smelting the volatilized sulfide gas through an electric furnace to recover tin, introducing tin-containing flue gas into the electric furnace to remelt the tin, controlling the system to flow out and cooling to obtain a tin product.
In the final slag of this example, the tin content was reduced from Sn2.56% to Sn0.39%.
Embodiment 3. Tin smelting method based on reuse of metallurgical waste slag, comprising the following steps:
1) Crushing tin-containing waste residues and a solvent, mixing, placing the crushed tin-containing waste residues and the crushed solvent into a smelting furnace, introducing gas to perform oxygen-enriched smelting to generate smelting flue gas, wherein the crushed tin-containing waste residues and the crushed solvent have a particle size of 2cm, the solvent is a mixture of limestone and fluorite, the mass ratio of the limestone to the fluorite is 5:1, the mass of the flux is 13% of the mass of the tin-containing waste residues, the temperature of the smelting furnace is 1250 ℃, and the oxygen content in the gas is 60%;
2) Adding a reducing agent into the solution obtained by smelting, mixing, and carrying out reduction smelting, wherein the reducing agent is charcoal, the reduction smelting temperature is 1200 ℃, and the added reducing agent is 30% of the mass of the solution.
3) Adding a vulcanizing agent into the solution obtained by reduction smelting for vulcanization volatilization, wherein the vulcanization temperature is 1200 ℃, the vulcanizing agent is pyrite and thiotin ore, the mass ratio of the pyrite to the thiotin ore is 2:1, gypsum is added into the vulcanizing agent as an auxiliary vulcanizing agent, the mass of the gypsum is 8% of the mass of the vulcanizing agent, the smelting flue gas is filtered and then reacts with oxygen and sodium hydroxide to generate sodium sulfate, and the sodium sulfate is added into the vulcanization step.
4) And condensing the gas volatilized by vulcanization to recover tin, and condensing the tin-containing flue gas to obtain a tin product.
In the final slag of this example, the tin content was reduced from Sn2.56% to Sn1.03%.
Example 4 tin smelting method based on metallurgical waste residue reuse, comprising the following steps:
1) Crushing tin-containing waste residues and a solvent, mixing, placing the crushed tin-containing waste residues and the crushed solvent into a smelting furnace, introducing gas to perform oxygen-enriched smelting to generate smelting flue gas, wherein the particle size of the crushed tin-containing waste residues and the crushed solvent is 3cm, the solvent is a mixture of limestone and fluorite, the mass ratio of the limestone to the fluorite is 3:2, the mass of the flux is 15% of the mass of the tin-containing waste residues, the temperature of the smelting furnace is 1200 ℃, and the oxygen content in the gas is 75%;
2) Adding a reducing agent into the solution obtained by smelting, mixing, and carrying out reduction smelting, wherein the reducing agent is coke, the reduction smelting temperature is 1300 ℃, and the added reducing agent is 20% of the mass of the solution.
3) Adding a vulcanizing agent into the solution obtained by reduction smelting, mixing, vulcanizing and volatilizing, wherein the vulcanizing temperature is 1300 ℃, the vulcanizing agent is pyrite, gypsum is added into the vulcanizing agent as an auxiliary vulcanizing agent, the mass of the gypsum is 10% of the mass of the vulcanizing agent, the smelted flue gas is filtered and then reacts with oxygen and sodium hydroxide to generate sodium sulfate, and the sodium sulfate is added into the vulcanizing step.
4) The gas evaporated by sulfuration passes through an absorption tower to recover tin.
In the final slag of this example, the tin content was reduced from Sn2.56% to Sn0.63%.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (8)

1.一种基于冶金废渣再利用的锡冶炼方法，其特征在于，包括以下步骤：1. A tin smelting method based on the recycling of metallurgical waste slag, characterized in that it comprises the following steps: 1)将含锡废渣和溶剂破碎后混合，置于熔炼炉内并通入气体进行富氧熔炼，产生熔炼烟气，溶剂为石灰石和萤石的混合物，熔炼炉温度1200-1300℃，气体中氧气含量≥50％；1) crushing the tin-containing waste slag and the solvent, mixing them, placing them in a smelting furnace and introducing gas for oxygen-enriched smelting to generate smelting fume, the solvent is a mixture of limestone and fluorite, the smelting furnace temperature is 1200-1300°C, and the oxygen content in the gas is ≥50%; 2)在上述熔炼得到的溶体中加入还原剂混合进行还原熔炼，还原剂为焦炭、木炭或煤粉，还原熔炼温度1100-1300℃；2) Adding a reducing agent to the melt obtained by the above smelting and mixing for reduction smelting, the reducing agent is coke, charcoal or coal powder, and the reduction smelting temperature is 1100-1300°C; 3)在上述还原熔炼得到的溶体中加入硫化剂混合进行硫化挥发；3) adding a sulfiding agent to the solution obtained by the reduction smelting to mix and volatilize; 4)硫化挥发的气体通过冷凝、电炉熔炼或吸收塔回收锡。4) The sulfide volatilized gas is recovered by condensation, electric furnace smelting or absorption tower. 2.根据权利要求1所述的基于冶金废渣再利用的锡冶炼方法，其特征在于：所述含锡废渣和熔剂破碎后的粒径为1-3cm。2. The tin smelting method based on the recycling of metallurgical waste slag according to claim 1 is characterized in that the particle size of the tin-containing waste slag and flux after crushing is 1-3 cm. 3.根据权利要求1所述的基于冶金废渣再利用的锡冶炼方法，其特征在于：所述的熔剂质量为含锡废渣质量的10-15％。3. The tin smelting method based on the recycling of metallurgical waste slag according to claim 1, characterized in that the mass of the flux is 10-15% of the mass of the tin-containing waste slag. 4.根据权利要求1所述的基于冶金废渣再利用的锡冶炼方法，其特征在于：所述石灰石和萤石的质量比是(5-3):(2-1)。4. The tin smelting method based on the recycling of metallurgical waste slag according to claim 1 is characterized in that the mass ratio of the limestone to the fluorite is (5-3):(2-1). 5.根据权利要求1所述的基于冶金废渣再利用的锡冶炼方法，其特征在于：所述的熔炼烟气经过过滤后与氧气和氢氧化钠反应生成硫酸钠，硫酸钠加入硫化步骤中。5. The tin smelting method based on the recycling of metallurgical waste slag according to claim 1 is characterized in that: the smelting fume is filtered and then reacted with oxygen and sodium hydroxide to generate sodium sulfate, and the sodium sulfate is added to the sulfurization step. 6.根据权利要求1所述的基于冶金废渣再利用的锡冶炼方法，其特征在于：所述的硫化温度为1000-1300℃。6. The tin smelting method based on recycling of metallurgical waste slag according to claim 1, characterized in that the sulfidation temperature is 1000-1300°C. 7.根据权利要求1所述的基于冶金废渣再利用的锡冶炼方法，其特征在于：所述的硫化剂为黄铁矿、硫铁矿和硫锡矿中的至少一种，硫化剂中加入石膏作为辅助硫化剂。7. The tin smelting method based on the recycling of metallurgical waste slag according to claim 1 is characterized in that the vulcanizing agent is at least one of pyrite, pyrite and tin sulfide, and gypsum is added to the vulcanizing agent as an auxiliary vulcanizing agent. 8.根据权利要求1所述的基于冶金废渣再利用的锡冶炼方法，其特征在于：加入的还原剂为溶体质量的15-35％。8. The tin smelting method based on the recycling of metallurgical waste slag according to claim 1, characterized in that the added reducing agent is 15-35% of the mass of the solution.
CN202411199361.3A 2024-08-29 2024-08-29 A tin smelting method based on recycling of metallurgical waste slag Pending CN119120903A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN120796615A (en) * 2025-09-03 2025-10-17 中国科学院过程工程研究所 Method for comprehensively utilizing multi-source solid waste

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN120796615A (en) * 2025-09-03 2025-10-17 中国科学院过程工程研究所 Method for comprehensively utilizing multi-source solid waste

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