工程科学学报，第37卷，第11期：1429-1433,2015年11月 Chinese Journal of Engineering,Vol.37,No.11:1429-1433,November 2015 D0l:10.13374/j.issn2095-9389.2015.11.006:http://journals..ustb.edu.cn NaPO,用于粗锑火法精炼过程除铅 叶龙刚，杨声海，唐朝波四，唐漠堂 中南大学治金与环境学院，长沙410083 ☒通信作者，E-mail:tangchaobo9043@163.com 摘要针对传统粗锑精炼工艺中除铅的难题，提出用NPO,作为除铅剂，生成磷酸盐渣浮于锑液表面除去的方法.用热 重一差热法和X射线衍射技术研究反应机理并进行粗锑除铅的条件实验.研究发现，P0与NaPO,在590℃时即开始吸热反 应，在850℃以下主要形成NaPh,(PO,),而在850℃以上主要形成NaPbPO,反应彻底.Ph0、Sb,03和NaPO混合物的反应 表明：在NaPO3量不足时，优先与Ph0反应，只有当NaPO,足量时才会与Sb,O3生成锑的非晶态玻璃.用NaNO3作为氧化 剂，在氮气保护下进行了除铅单因素实验，考察反应时间和温度、NPO,和NaNO,加入量对结果的影响.在最优条件下精锑 含铅0.047%，除铅率98.90%. 关键词锑治金：偏磷酸钠：精炼：除铅 分类号TF818 Lead removal from crude antimony in the pyrometallurgical refining process by using NaPO YE Long-gang,YANG Sheng-hai,TANG Chao-bo,TANG Mo-tang School of Metallurgy and Environment,Central South University,Changsha 410083,China Corresponding author,E-mail:tangchaobo9043@163.com ABSTRACT In order to solve the problem of lead removal from crude antimony in the traditional antimony refining process,NaPO was introduced as a lead elimination reagent to generate phosphate slag and the slag was removed by floating on the surface of liquid antimony.The reaction mechanisms were clarified by thermogravimetric-differential thermal analysis and X-ray diffraction analysis and removal of Pb from crude Sb was investigated by condition experiment.It is found that PbO and NaPO,begin an endothermic reaction at590℃and mainly form NaPb,(PO,）,and NaPbPO,below850℃and above850℃，respectively.The reaction products of the mixture of PbO,Sb2O;and NaPO,show that NaPO,preferentially reacts with PbO when NaPO3 is insufficient,and amorphous antimo- ny glass will generate only with enough NaPO.Single-factor experiments were taken with NaNO:as an oxidizing agent under nitrogen. Reaction time,temperature,NaPO,and NaNO,amounts were considered for smelting results.Under the optimal condition,the con- tent of lead in refined antimony is 0.047%and 98.90%of lead is removed. KEY WORDS antimony metallurgy:sodium metaphosphate;refining:lead removal 中国是世界上最大的金属锑生产国，锑矿储量丰除铅 富，湖南锡矿山是世界著名的锑都·.炼锑的主要原 Hassam和Raghavan分别研究了Pb-Sb二元 料是硫化矿，有辉锑矿和脆硫铅锑矿两种四，这些矿都 系相图，证明铅在锑内最大的溶解度介于1.5%~ 伴生有铅，由这两种矿治炼得到的粗锑含铅0.1%~ 2.7%之间，因此锑内如含有少量的铅采用一般的方法 5%,没有达到商品锑的要求(0.1%以下)，需要精炼 不容易除掉.传统的火法除铅方法有硫化、氯化和真 收稿日期：2014-06-30 基金项目：国家自然科学基金资助项目(51234009,51104128)工程科学学报，第 37 卷，第 11 期: 1429--1433，2015 年 11 月 Chinese Journal of Engineering，Vol． 37，No． 11: 1429--1433，November 2015 DOI: 10． 13374 /j． issn2095--9389． 2015． 11． 006; http: / /journals． ustb． edu． cn NaPO3 用于粗锑火法精炼过程除铅 叶龙刚，杨声海，唐朝波，唐谟堂 中南大学冶金与环境学院，长沙 410083  通信作者，E-mail: tangchaobo9043@ 163． com 摘 要 针对传统粗锑精炼工艺中除铅的难题，提出用 NaPO3 作为除铅剂，生成磷酸盐渣浮于锑液表面除去的方法． 用热 重--差热法和 X 射线衍射技术研究反应机理并进行粗锑除铅的条件实验． 研究发现，PbO 与 NaPO3 在 590 ℃时即开始吸热反 应，在 850 ℃以下主要形成 NaPb4 ( PO4 ) 3，而在 850 ℃以上主要形成 NaPbPO4，反应彻底． PbO、Sb2O3 和 NaPO3 混合物的反应 表明: 在 NaPO3 量不足时，优先与 PbO 反应，只有当 NaPO3 足量时才会与 Sb2O3 生成锑的非晶态玻璃． 用 NaNO3 作为氧化 剂，在氮气保护下进行了除铅单因素实验，考察反应时间和温度、NaPO3 和 NaNO3 加入量对结果的影响． 在最优条件下精锑 含铅 0. 047% ，除铅率 98. 90% ． 关键词 锑冶金; 偏磷酸钠; 精炼; 除铅 分类号 TF818 Lead removal from crude antimony in the pyrometallurgical refining process by using NaPO3 YE Long-gang，YANG Sheng-hai，TANG Chao-bo ，TANG Mo-tang School of Metallurgy and Environment，Central South University，Changsha 410083，China  Corresponding author，E-mail: tangchaobo9043@ 163． com ABSTＲACT In order to solve the problem of lead removal from crude antimony in the traditional antimony refining process，NaPO3 was introduced as a lead elimination reagent to generate phosphate slag and the slag was removed by floating on the surface of liquid antimony． The reaction mechanisms were clarified by thermogravimetric-differential thermal analysis and X-ray diffraction analysis and removal of Pb from crude Sb was investigated by condition experiment． It is found that PbO and NaPO3 begin an endothermic reaction at 590 ℃ and mainly form NaPb4 ( PO4 ) 3 and NaPbPO4 below 850 ℃ and above 850 ℃，respectively． The reaction products of the mixture of PbO，Sb2O3 and NaPO3 show that NaPO3 preferentially reacts with PbO when NaPO3 is insufficient，and amorphous antimo￾ny glass will generate only with enough NaPO3 ． Single-factor experiments were taken with NaNO3 as an oxidizing agent under nitrogen． Ｒeaction time，temperature，NaPO3 and NaNO3 amounts were considered for smelting results． Under the optimal condition，the con￾tent of lead in refined antimony is 0. 047% and 98. 90% of lead is removed． KEY WOＲDS antimony metallurgy; sodium metaphosphate; refining; lead removal 收稿日期: 2014--06--30 基金项目: 国家自然科学基金资助项目( 51234009，51104128) 中国是世界上最大的金属锑生产国，锑矿储量丰 富，湖南锡矿山是世界著名的锑都［1--2］． 炼锑的主要原 料是硫化矿，有辉锑矿和脆硫铅锑矿两种［3］，这些矿都 伴生有铅，由这两种矿冶炼得到的粗锑含铅 0. 1% ～ 5% ，没有达到商品锑的要求( 0. 1% 以下) ，需要精炼 除铅． Hassam［4］和 Ｒaghavan［5］ 分别研究了 Pb--Sb 二元 系相图，证明铅在锑内最大的溶解度介于 1. 5% ～ 2. 7% 之间，因此锑内如含有少量的铅采用一般的方法 不容易除掉． 传统的火法除铅方法有硫化、氯化和真