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Article(id=1241321700118295313, tenantId=1146029695717560320, journalId=1235980550691926019, issueId=1241321691524158287, articleNumber=null, orderNo=null, doi=10.3969/j.issn.0253-6099.2025.02.023, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1728921600000, receivedDateStr=2024-10-15, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1773883755950, onlineDateStr=2026-03-19, pubDate=1743436800000, pubDateStr=2025-04-01, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1773883755950, onlineIssueDateStr=2026-03-19, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1773883755950, creator=13701087609, updateTime=1773883755950, updator=13701087609, issue=Issue{id=1241321691524158287, tenantId=1146029695717560320, journalId=1235980550691926019, year='2025', volume='45', issue='2', pageStart='1', pageEnd='204', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1773883753901, creator=13701087609, updateTime=1773884632018, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1241325374676726363, tenantId=1146029695717560320, journalId=1235980550691926019, issueId=1241321691524158287, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1241325374676726364, tenantId=1146029695717560320, journalId=1235980550691926019, issueId=1241321691524158287, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=130, endPage=134, ext={EN=ArticleExt(id=1241321700588057403, articleId=1241321700118295313, tenantId=1146029695717560320, journalId=1235980550691926019, language=EN, title=Oxidation Behavior of Thallium Sulfide During Roasting of Zinc Concentrate, columnId=1236276106727321817, journalTitle=Mining and Metallurgical Engineering, columnName=METALLURGY, runingTitle=null, highlight=null, articleAbstract=

In order to investigate the reaction behavior of associated thallium sulfide in zinc concentrate during fluidized roasting, thermodynamic calculation and verification experiments were conducted for the oxidation process of thallium sulfide. Firstly, the volatilization of thallium chloride, thallium oxide, metallic thallium and thallium sulfide were analyzed based on data retrieval and calculation, and the volatilization of those four matters was determined in the following descending order: Tl2O>TlCl>Tl2S>Tl. Then, the equilibrium analysis and the calculation of Gibbs free energy change of the Tl2S-O2 system were conducted. It is shown that Tl2S volatilizes violently in an inert atmosphere as temperature rises, and decomposes into Tl and sulfur vapor after temperature is above 1 000 ℃. However, in an oxidizing atmosphere, Tl2S begins to generate a large quantities of Tl2SO4 after the temperature reaches 100 ℃, and a few of Tl2S begins to decompose into SO2 and Tl2O after temperature is above 1 000 ℃. No interaction occurs between Tl2S and ZnO. In the practical roasting process, Tl2S is completely converted into Tl2SO4 and remains stable in the calcine at the temperature above 800 ℃, which can be intensively removed in the subsequent open-circuit of leaching and purification process.

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为查明锌精矿中伴生硫化铊在沸腾焙烧过程中的反应行为，对硫化铊的氧化过程进行了热力学计算模拟和试验验证。首先通过数据检索与计算分析了氯化铊、氧化铊、金属铊、硫化铊等铊的4种主要物质的挥发特性，明确了4种主要物质的挥发性顺序为：Tl2O>TlCl>Tl2S>Tl；其次进行了Tl2S-O2体系的反应平衡分析和吉布斯自由能变计算。结果表明：在无氧环境中，随着温度升高，Tl2S发生强烈挥发，1 000 ℃后分解产生铊和硫蒸气；在氧化性气氛中，Tl2S从100 ℃开始大量生成Tl2SO4，1 000 ℃后开始少量分解生成SO2和Tl2O；Tl2S不与ZnO发生交互反应。实际焙烧过程中，800 ℃以后Tl2S全部转化为Tl2SO4，并稳定存在于焙砂中，可在后续浸出-净化过程中进行集中开路去除。

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林文军（1978—），男，湖南武冈人，高级工程师，主要从事有色冶金、资源综合回收及新材料等方面的研究。E-mail：

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林文军（1978—），男，湖南武冈人，高级工程师，主要从事有色冶金、资源综合回收及新材料等方面的研究。E-mail：

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林文军（1978—），男，湖南武冈人，高级工程师，主要从事有色冶金、资源综合回收及新材料等方面的研究。E-mail：

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The Chinese Journal of Nonferrous Metals, 2024, 34(6): 2043-2058., articleTitle=Research status and development trend of causes of thallium pollution in surface water and soil environment, refAbstract=null)], funds=[Fund(id=1241327688913318885, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241321700118295313, awardId=2023YFC3904100, language=CN, fundingSource=国家重点研发计划(2023YFC3904100), fundOrder=null, country=null)], companyList=[AuthorCompany(id=1241327680549876300, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241321700118295313, xref=null, ext=[AuthorCompanyExt(id=1241327680558264911, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241321700118295313, companyId=1241327680549876300, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=Zhuzhou Smelting Group Co, Ltd, Zhuzhou 412000, Hunan, China), AuthorCompanyExt(id=1241327680566653519, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241321700118295313, companyId=1241327680549876300, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=株洲冶炼集团股份有限公司，湖南　株洲　412000)])], figs=[ArticleFig(id=1241327686501593914, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241321700118295313, language=EN, label=Fig.1, caption=Vapor pressure of metal thallium and thallium compounds, figureFileSmall=LuklZnv+d/AxiBEDEW8hRw==, figureFileBig=DP3pujO06corAXdAQFplUg==, tableContent=null), ArticleFig(id=1241327686619034435, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241321700118295313, language=CN, label=图1, caption=金属铊和铊化合物的蒸气压数据, figureFileSmall=LuklZnv+d/AxiBEDEW8hRw==, figureFileBig=DP3pujO06corAXdAQFplUg==, tableContent=null), ArticleFig(id=1241327686749057867, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241321700118295313, language=EN, label=Fig.2, caption=Equilibrium distribution of oxidative volatilization of Tl2S, figureFileSmall=wvieg8Ee6XJxVCm9uwXD5w==, figureFileBig=h28aM0P6mmuHtkEjQelAiw==, tableContent=null), ArticleFig(id=1241327686858109777, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241321700118295313, language=CN, label=图2, caption=Tl2S的氧化挥发反应平衡分布

（a）无氧；（b）n（O2）=0.5 mol；（c）n（O2）=1.0 mol；（d）n（O2）=2.0 mol

, figureFileSmall=wvieg8Ee6XJxVCm9uwXD5w==, figureFileBig=h28aM0P6mmuHtkEjQelAiw==, tableContent=null), ArticleFig(id=1241327687042659169, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241321700118295313, language=EN, label=Fig.3, caption=Relationships between ΔGθ and T of reactions（2）～（5）, figureFileSmall=G4ohT9KrkmnQBb/20UTfxA==, figureFileBig=KRubo9VX+N4AQd7n9yAP8w==, tableContent=null), ArticleFig(id=1241327687168488296, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241321700118295313, language=CN, label=图3, caption=反应（2）～（5）的吉布斯自由能变与温度的关系, figureFileSmall=G4ohT9KrkmnQBb/20UTfxA==, figureFileBig=KRubo9VX+N4AQd7n9yAP8w==, tableContent=null), ArticleFig(id=1241327687306900336, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241321700118295313, language=EN, label=Fig.4, caption=Equilibrium simulation results of interactive reaction between Tl2S and ZnO, figureFileSmall=NMgzpittGr+JdUElX3WCPw==, figureFileBig=vaGQKPGijkPB8tIwxlOMQg==, tableContent=null), ArticleFig(id=1241327687457895292, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241321700118295313, language=CN, label=图4, caption=Tl2S与ZnO的交互反应平衡模拟计算结果

（a）n（ZnO）=1 mol；（b）n（ZnO）=2 mol

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tableContent=null), ArticleFig(id=1241327687969600421, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241321700118295313, language=CN, label=图6, caption=不同温度下焙烧产物XRD图谱, figureFileSmall=wh3l4HEMk+LuCBBtJJY2iQ==, figureFileBig=sRvwC2ELUP4368Odp5mW3g==, tableContent=null), ArticleFig(id=1241327688057680815, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241321700118295313, language=EN, label=Fig.7, caption=Relationships between mass of roasted products and temperature, figureFileSmall=CTfs82XXQiNZ2qfMoMicDg==, figureFileBig=aX5S6G2e1cuWtpvi/rHyHA==, tableContent=null), ArticleFig(id=1241327688166732729, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241321700118295313, language=CN, label=图7, caption=焙烧产物质量与温度的关系, figureFileSmall=CTfs82XXQiNZ2qfMoMicDg==, figureFileBig=aX5S6G2e1cuWtpvi/rHyHA==, tableContent=null), ArticleFig(id=1241327688288367554, tenantId=1146029695717560320, journalId=1235980550691926019, 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锌精矿焙烧过程中硫化铊氧化行为研究
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林文军
矿冶工程杂志 | 冶金 2025,45(2): 130-134
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矿冶工程杂志 | 冶金 2025, 45(2): 130-134
锌精矿焙烧过程中硫化铊氧化行为研究
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林文军
作者信息
  • 株洲冶炼集团股份有限公司，湖南　株洲　412000

    • 林文军（1978—），男，湖南武冈人，高级工程师，主要从事有色冶金、资源综合回收及新材料等方面的研究。E-mail：

Oxidation Behavior of Thallium Sulfide During Roasting of Zinc Concentrate
Wenjun LIN
Affiliations
  • Zhuzhou Smelting Group Co, Ltd, Zhuzhou 412000, Hunan, China
出版时间: 2025-04-01 doi: 10.3969/j.issn.0253-6099.2025.02.023
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摘要
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为查明锌精矿中伴生硫化铊在沸腾焙烧过程中的反应行为，对硫化铊的氧化过程进行了热力学计算模拟和试验验证。首先通过数据检索与计算分析了氯化铊、氧化铊、金属铊、硫化铊等铊的4种主要物质的挥发特性，明确了4种主要物质的挥发性顺序为：Tl2O>TlCl>Tl2S>Tl；其次进行了Tl2S-O2体系的反应平衡分析和吉布斯自由能变计算。结果表明：在无氧环境中，随着温度升高，Tl2S发生强烈挥发，1 000 ℃后分解产生铊和硫蒸气；在氧化性气氛中，Tl2S从100 ℃开始大量生成Tl2SO4，1 000 ℃后开始少量分解生成SO2和Tl2O；Tl2S不与ZnO发生交互反应。实际焙烧过程中，800 ℃以后Tl2S全部转化为Tl2SO4，并稳定存在于焙砂中，可在后续浸出-净化过程中进行集中开路去除。

铊  /  氧化  /  平衡模拟  /  物相分析  /  硫化铊  /  氧化铊  /  热力学计算  /  锌冶炼  /  沸腾焙烧

In order to investigate the reaction behavior of associated thallium sulfide in zinc concentrate during fluidized roasting, thermodynamic calculation and verification experiments were conducted for the oxidation process of thallium sulfide. Firstly, the volatilization of thallium chloride, thallium oxide, metallic thallium and thallium sulfide were analyzed based on data retrieval and calculation, and the volatilization of those four matters was determined in the following descending order: Tl2O>TlCl>Tl2S>Tl. Then, the equilibrium analysis and the calculation of Gibbs free energy change of the Tl2S-O2 system were conducted. It is shown that Tl2S volatilizes violently in an inert atmosphere as temperature rises, and decomposes into Tl and sulfur vapor after temperature is above 1 000 ℃. However, in an oxidizing atmosphere, Tl2S begins to generate a large quantities of Tl2SO4 after the temperature reaches 100 ℃, and a few of Tl2S begins to decompose into SO2 and Tl2O after temperature is above 1 000 ℃. No interaction occurs between Tl2S and ZnO. In the practical roasting process, Tl2S is completely converted into Tl2SO4 and remains stable in the calcine at the temperature above 800 ℃, which can be intensively removed in the subsequent open-circuit of leaching and purification process.

thallium  /  oxidation  /  equilibriumsimulation  /  phaseanalysis  /  thalliumsulfide  /  thalliumoxide  /  thermodynamic calculation  /  zinc smelting  /  fluidized roasting
林文军. 锌精矿焙烧过程中硫化铊氧化行为研究. 矿冶工程杂志, 2025 , 45 (2) : 130 -134 . DOI: 10.3969/j.issn.0253-6099.2025.02.023
Wenjun LIN. Oxidation Behavior of Thallium Sulfide During Roasting of Zinc Concentrate[J]. Mining and Metallurgical Engineering, 2025 , 45 (2) : 130 -134 . DOI: 10.3969/j.issn.0253-6099.2025.02.023
正文
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铊是自然界存在的稀有分散元素，地壳中的平均含量约为1 g/t[1]。铊是一种伴生元素，几乎不单独成矿。在中低温热液环境中，硫化物矿物（如黄铁矿、方铅矿）广泛形成。铊的挥发性使其在热液环境中易于迁移，而硫的还原性环境（如H2S的存在）会促进铊的硫化反应，因此铊主要以分散状态的同晶形杂质存在于铅、锌、铁、铜等金属的硫化矿中[2-3]，当其中的铊富集到一定程度时，硫化物结构提供了更稳定的晶格环境，使其能够形成独立硫化矿物。同时基于软硬酸碱理论，Tl+属于软酸，而S2-是典型的软碱，二者容易结合形成稳定化合物。在金属锌、铅、铜的矿石提取过程中，首先是氧化过程，硫化铊发生系列物理化学反应进入后续物料中。大量研究表明，铊的氧化物氧化铊、氧化亚铊挥发性强，在铜、铅、锌硫化物精矿焙烧、烧结和冶炼时大部分铊挥发进入烟尘[4-5]。例如，炼铅时60%～70%的铊进入烧结、焙烧烟尘中；炼锌时50%以上铊被氧化进入焙砂，并进一步进入浸出流程中[6]。由于原矿中铊含量低，铊的具体转化机理和反应行为尚不明确[7-8]。
在湿法炼锌过程中，铊（Tl）作为一种剧毒且化学性质活泼的重金属杂质，对生产流程、产品质量及环境安全均构成严重威胁。其危害主要体现在以下方面。①影响硫酸锌溶液净化，铊在酸性浸出阶段（pH值1～2）易以Tl+形式溶出，与锌离子共存于溶液中。Tl+/Tl标准电极电位为-0.34 V，接近Zn2+/Zn的标准电极电位（-0.76 V），导致后续锌粉置换除杂时，铊优先被置换析出，形成微米级金属颗粒。这些颗粒会包裹锌粉表面，显著降低锌粉对钴、铜、镍、镉等杂质的脱除效率，导致锌粉投加量增加20%以上，直接增加生产成本[9-10]。同时，铊的金属态、氧化物态均可反复溶解，形成锌铊微电池，造成阴极锌返溶，电流效率下降3%～5%。②污染阴极锌品质，在锌电解沉积阶段，Tl+在阴极还原为金属铊，与锌共沉积形成晶格缺陷，导致阴极锌表面出现灰斑、疏松结瘤。同时铊离子吸附在析出锌阴极表面，破坏双电层结构，诱发锌枝晶异常生长，轻则降低产品致密度，重则引发电极短路，导致停槽检修。③增加系统循环污染与环保压力，铊在湿法炼锌体系中每经过一次溶液循环，铊浓度可提升5%～8%，最终在电解废液、浸出渣、阳极泥、废水等多相介质中扩散[11]。其剧毒性（人体致死剂量小于1 g）对车间操作人员构成直接健康威胁，可能引发严重环境事件。④除铊成本高，目前除铊有硫化法、活性炭吸附和离子交换法。硫化法需维持溶液pH>4并添加过量Na2S，会造成锌沉淀损失；活性炭对Tl+吸附容量仅为8～12 mg/g，过程易受干扰；离子交换法的树脂成本高，再生废液处理难度大。
当前锌的主要冶炼方法是沸腾焙烧-酸浸提取工艺[12]，在闪锌矿焙烧时，氧化性气氛强、焙烧温度高，焙烧炉内发生剧烈氧化、分解、挥发等反应。锌精矿中铊含量极低、难以检测，目前只知道铊主要通过氧化反应进入焙砂和烟气，并在浸出过程中进入湿法系统，但具体的物相转化形态和稳定边界条件并不明确。鉴于铊对湿法炼锌过程的如上影响，如何进行强化焙烧使铊尽量富集于一种产物形态集中回收，是值得深入研究的问题。本文通过热力学计算并结合实验研究，对硫化铊的挥发/氧化行为进行分析，以明确铊在氧化焙烧过程中的反应行为和分布形态。
1　硫化铊氧化挥发热力学
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1.1　铊及铊化合物的蒸气压
铊金属及化合物均易挥发。查阅和计算了金属铊和铊化合物的蒸气压数据，如图1所示。可以看出，400 ℃后氧化铊饱和蒸气压直线上升，发生强烈挥发。其后依次是氯化铊、硫化铊和金属铊，4种化合物达到常压沸腾的温度分别为486、720、1 172、1 457 ℃，挥发性大小顺序为：Tl2O>TlCl>Tl2S>Tl。铊的地球化学研究[13]表明，闪锌矿中铊主要以硫化物形态存在，而沸腾炉内为强氧化性气氛，理论上锌精矿中的硫化铊可被快速氧化，并以氧化铊形式挥发进入烟尘；而在多膛炉或回转窑处理锌浸出渣或锌烟灰时，炉内为还原性气氛，且烟灰中含有一定量氯和氟，可以控制原料中的氯含量，使之以TlCl形式挥发进入烟尘，操作温度控制在720 ℃以上即可沸腾挥发。以锌原矿冶炼为例，闪锌矿为主要原料，其中铊以硫化铊形式赋存，研究其在沸腾焙烧过程中的反应行为，对认清铊在后续浸出、净化、渣处理过程中铊的分布具有重要意义。
1.2　Tl2S氧化挥发热力学平衡
因铊主要以分散状态的同晶形杂质存在于硫化矿中，这里主要讨论硫化铊（Tl2S）的氧化挥发热力学。采用HSC热力学软件对硫化铊的挥发行为进行了平衡模拟，固定Tl2S起始物质的量为1 mol，逐步增加O2量时Tl2S的氧化挥发反应平衡分布情况见图2。从图2可以看出，Tl2S在无氧环境下于800 ℃开始明显挥发，到1 200 ℃时基本呈气态存在，这与图1蒸气压数据较为一致；但温度超过1 000 ℃后Tl2S开始发生分解反应，生成了金属铊和元素硫蒸气。随着氧气量增加，反应开始变得复杂。n（O2）=0.5 mol时，Tl2SO4首先生成，温度升到800 ℃时，大量生成金属铊和二氧化硫，联想铅精矿在氧化焙烧过程中可以直接产出金属铅以及铅铊的同源性，可推断此时发生了铊的交互反应；此后进一步升高温度，硫化铊开始大量挥发，以Tl2S（g）形式逸出系统并氧化；另外，此时温度高，金属铊也大量挥发，Tl2O（g）和Tl（g）生成量开始增加。n（O2）=1.0 mol时，Tl2SO4一开始即大量生成，此后大量生成金属铊、氧化铊和铊蒸气。n（O2）=2.0 mol时，一开始即大量生成Tl2SO4，由于氧气过量，Tl2S都被氧化生成Tl2SO4，Tl2SO4很稳定，1000 ℃后才开始少量分解，生成SO2和Tl2O。沸腾焙烧在强氧化性气氛中进行，操作温度900～1 000 ℃，铊主要生成硫酸铊进入焙砂，并可能在后续浸出过程中进入溶液。
Tl2S的主要反应如下：
反应（2）～（5）的吉布斯自由能变与温度的关系如图3所示。可以看出，反应（4）即Tl2S与Tl2O的交互反应ΔGθ一直为正，无法通过该反应生成金属铊；其他3个反应的ΔGθ在0～1 200 ℃范围内均为负值，具有较大的反应倾向，因此Tl2S可氧化为金属铊、硫酸铊和氧化铊，其中反应（2）的ΔGθ随着温度升高而正移，即升高温度不利于Tl2SO4的生成，这与平衡分析结果一致，即升高温度会促进Tl2SO4的分解。
1.3　Tl2S与ZnO交互反应热力学平衡
考虑到沸腾炉中有大量ZnO存在，可能影响铊的转化行为，因此进一步计算了Tl2S与ZnO交互反应的热力学平衡。固定n（Tl2S）=1 mol、n（O2）=1 mol，增加ZnO的量，Tl2S与ZnO的交互反应平衡模拟计算结果如图4所示。无论是ZnO和Tl2S物质的量相等，还是ZnO过量，Tl2S的反应行为较为一致，即开始时铊全部生成了Tl2SO4，此后一直稳定存在，直到1 100 ℃后开始逐渐分解，生成Tl2O。因此Tl2S与ZnO的交互反应很弱，在氧化性气氛中，Tl2S几乎不与ZnO反应，可独立完成氧化脱硫生成稳定的Tl2SO4，不受炉内锌精矿焙烧产物的影响。
2　Tl2S氧化挥发试验研究
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以纯硫化铊为原料，对Tl2S的氧化过程进行分析表征和试验研究。升温速度10 ℃/min时，Tl2S在空气气氛下的TG-DSC-DTG结果见图5。从图5可以看出，153.6～251.2 ℃段Tl2S质量变化为3.14%，同时DSC曲线上出现了明显的放热峰，结合热力学分析可知，这是Tl2S氧化成了Tl2SO4，质量增加且氧化放热；而在447.9～541.5 ℃段质量变化为-2.91%，伴随着弱吸热峰出现，即出现轻度挥发损失。此后质量变化不大，但从800 ℃开始质量快速减少，结合热力学分析可知，此时可能发生了大量的氧化挥发。
以TG-DSC结果为指导，每次取1 g样品，在箱式炉中于空气气氛中进行不同温度下的Tl2S氧化焙烧试验，焙烧时间1 h。对焙烧产物进行了XRD检测，结果如图6所示。可以看出，自500 ℃开始，产物中出现大量Tl2SO4衍射峰，但此时氧化反应不完全，仍有部分Tl2S的峰残留；升温至800 ℃后，产物基本只有Tl2SO4，说明此时氧化很充分。这比热力学分析得到的温度高，是因为氧化反应在低温下较缓慢，反应活性较低，800 ℃后才能快速反应。
进一步记录了焙烧产物质量与温度的变化，如图7所示。可以看出，500～700 ℃范围内，随着温度升高，样品增重缓慢，800 ℃后样品快速增重。这与XRD分析结果较为一致，800 ℃后Tl2S快速转变成Tl2SO4，增重明显。至1 000 ℃时质量增加37.21%，这与Tl2S完全转化成Tl2SO4的理论增重较为一致。
950 ℃下焙烧产物的SEM-EDS分析结果如图8所示。产物颗粒较为疏松多孔，呈现均匀的形态分布，氧化完全。其中主要含有O、Tl、S，三者的原子比接近4∶2∶1，即Tl2SO4的成分组成。以上纯物质的热力学研究和试验表征均证明了Tl2S在沸腾炉内焙烧产物全为Tl2SO4。
对某冶炼厂152 m2沸腾焙烧炉的锌焙砂进行取样，进行了XPS分析，结果如图9所示。铊含量较低，导致峰强较弱，但对比发现Tl4f的特征吸收峰在119.5 eV处，与铊的硫酸盐特征峰所在位置较为接近，因此实际锌精矿在焙烧过程中伴生的Tl2S转变为Tl2SO4，稳定存在于焙砂中，从而在后续浸出过程中进入浸出液，需要在净化段进行集中除去。当前的锌精矿焙烧温度保持在1 050 ℃左右，根据生产物料平衡对焙砂和烟气取样分析，发现焙烧过程中92%的铊进入了焙砂，8%的铊进入烟气。可通过降低温度、细化物料粒度、快速氧化等使铊尽量多以Tl2SO4形式进入焙砂，减少在烟气中的分布，集中从浸出溶液中开路去除。
3　结论
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1）铊的主要化合物挥发性顺序为：Tl2O>TlCl>Tl2S>Tl；在锌精矿沸腾焙烧和浸出渣挥发窑处理过程中，可通过调控氧化和氯化气氛实现铊的分离富集。
2）热力学分析结果表明，在无氧环境中，随着温度升高，Tl2S发生强烈挥发，1 000 ℃后分解产生铊和硫蒸气；在氧化性气氛中，Tl2S从100 ℃开始转化成Tl2SO4，到1 000 ℃后开始少量分解生成SO2和Tl2O；Tl2S不与ZnO发生交互反应。实际焙烧过程中，800 ℃以后Tl2S全部转化为Tl2SO4，并稳定存在于焙砂中，可在后续浸出-净化过程中进行集中开路去除。
基金
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  • 国家重点研发计划(2023YFC3904100)
文献
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2025年第45卷第2期
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doi: 10.3969/j.issn.0253-6099.2025.02.023
  • 接收时间：2024-10-15
  • 首发时间：2026-03-19
  • 出版时间：2025-04-01
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  • 收稿日期：2024-10-15
基金
国家重点研发计划(2023YFC3904100)
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    株洲冶炼集团股份有限公司，湖南　株洲　412000
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2种不同金属材料的力学参数
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Family		 属数
Number of
genus		 种数
Number of
species		 占总种数比例
Percentage of
total species (%)		 属
Genus		 种数
Number of
species		 占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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