简介概要

无污染砷碱渣处理技术工业试验

来源期刊:中南大学学报(自然科学版)2005年第2期

论文作者:仇勇海 卢炳强 陈白珍 钟宇 傅伟 杨一乾

文章页码:234 - 237

关键词:砷碱渣;废渣处理;环境保护

Key words:slag of arsenic and soda; waste disposal; environmental protection

摘    要:以锑冶炼产生的砷碱渣为原料,在80℃下,搅拌约2 h浸出脱锑;在脱锑后液中通入二氧化碳气体,脱除碳酸盐;调整脱碱后液的pH值,在酸性条件下加入适量的硫化钠脱除砷。“无污染砷碱渣处理技术”工业试验结果表明:锑和铅的回收率分别达到99.0%和99.6%;砷、碱和硫酸钠的浸出率分别达到90%,99%和100%;碳酸盐中碱含量达到95%,砷含量在1%左右;砷硫化物中砷含量达到37%;在脱砷过程中产生的少量硫化氢采用氢氧化钠溶液吸收,吸收液返回脱砷系统;水溶液闭路循环,无废水外排;锑精矿、碳酸盐返回锑冶炼;砷硫化物、硫酸钡作为产品销售。采用该技术无废气、废水、废渣产生,工艺流程简单,操作条件容易控制,设备投资少。

Abstract: By stirring the mixture of slag of arsenic and soda in smelting antimony at 80℃ for about 2 h, the mixture was filtered so as to remove the antimony. Then the liquid after removing antimony was blown by CO2in order to remove the carbonic salt. The pH value of the mixture after removing the carbonic salt was adjusted and the appropriate Na2S was added to the mixture in order to remove the arsenic. The commercial scale test was conducted for anti-pollution treating.The results indicate that the recovery rate of antimony and lead is 99.0% and 99.6%, respectively. The leach rate of arsenic, soda and sodium sulfate is 90%,99% and 100%, respectively. The content of soda in carbonic salt reaches 95% and the content of arsenic is about 1%; the content of arsenic in arsenide sulfur reaches 37%. Sodium hydroxide is used to absorb the little hydrogen sulfide which is produced in the process of removing arsenic,and the absorbing liquid goes back to removing arsenic system. The water solution is closed circularly, and there is no waste water pushing outside.Concentrate antimony and carbonate go back to antimony for smelting,arsenide sulfur and barium sulfate are as products for saling. The waste gas, waste water and waste slag aren′t produced using the technique. The technological process is simple,the handling condition can be easily controlled, and the investment in equipment is small.



详情信息展示

无污染砷碱渣处理技术工业试验

 仇勇海1,卢炳强2,陈白珍3,钟 宇2,傅 伟1,杨一乾3

(1.中南大学 信息物理工程学院,湖南 长沙,410083;
2.广鑫冶炼有限公司,广东 郁南,527100;
3.中南大学 冶金科学与工程学院,湖南 长沙,410083)

 摘要: 以锑冶炼产生的砷碱渣为原料,在80 ℃下,搅拌约2 h浸出脱锑;在脱锑后液中通入二氧化碳气体,脱除碳酸盐;调整脱碱后液的pH值,在酸性条件下加入适量的硫化钠脱除砷。“无污染砷碱渣处理技术”工业试验结果表明:锑和铅的回收率分别达到99.0%和99.6%;砷、碱和硫酸钠的浸出率分别达到90%,99%和100%;碳酸盐中碱含量达到95%,砷含量在1%左右;砷硫化物中砷含量达到37%;在脱砷过程中产生的少量硫化氢采用氢氧化钠溶液吸收,吸收液返回脱砷系统;水溶液闭路循环,无废水外排;锑精矿、碳酸盐返回锑冶炼;砷硫化物、硫酸钡作为产品销售。采用该技术无废气、废水、废渣产生,工艺流程简单,操作条件容易控制,设备投资少。
关键词: 砷碱渣; 废渣处理; 环境保护
中图分类号:X75 文献标识码:A 文章编号: 1672-7207(2005)02-0234-04

Commercial Scale Test of Anti-pollution Control Technique for Slag of Arsenic and Soda

QIU Yong-hai1, LU Bing-qiang2, CHEN Bai-zhen3, ZHONG Yu2, FU Wei1, YANG Yi-qian3

(1.School of Info-physics and Geomatics Engineering, Central South University, Changsha 410083, China;
2.Guangxin Metallurgy Limited, Yunan 527100, China;
3.School of Metallurgical Science and Engineering,Central South University, Changsha 410083, China)

Abstract:By stirring the mixture of slag of arsenic and soda in smelting antimony at 80 ℃ for about 2 h, the mixture was filtered so as to remove the antimony. Then the liquid after removing antimony was blown by CO2 in order to remove the carbonic salt. The pH value of the mixture after removing the carbonic salt was adjusted and the appropriate Na2S was added to the mixture in order to remove the arsenic. The commercial scale test was conducted for anti-pollution treating. The results indicate that the recovery rate of antimony and lead is 99.0% and 99.6%, respectively. The leach rate of arsenic, soda and sodium sulfate is 90%,99% and 100%, respectively. The content of soda in carbonic salt reaches 95% and the content of arsenic is about 1%; the content of arsenic in arsenide sulfur reaches 37%. Sodium hydroxide is used to absorb the little hydrogen sulfide which is produced in the process of removing arsenic,and the absorbing liquid goes back to removing arsenic system. The water solution is closed circularly, and there is no waste water pushing outside.Concentrate antimony and carbonate go back to antimony for smelting,arsenide sulfur and barium sulfate are as products for saling. The waste gas, waste water and waste slag aren′t produced using the technique. The technological process is simple,the handling condition can be easily controlled, and the investment in equipment is small.
Key words: slag of arsenic and soda; waste disposal; environmental protection 

   在锑冶炼中,通常采用锑的碱性精练方法即加碱鼓风的方法对粗锑进行精练,产出精锑和砷碱渣。广鑫冶炼有限公司的砷碱渣的主要物质成分(质量分数)为:锑:20.41%;铅:29.96%;砷:9.80%;碱:20.84%;硫酸钠:1.99%。锡矿山矿务局的砷碱渣中锑含量达到30%~40%,砷3%~5%[1]。锡矿山矿务局在1990年采用反射炉熔炼法处理砷碱渣[2],采用该方法虽然较好地回收了锑,但未能把砷从锑冶炼系统中完全消除。

湿法处理砷碱渣的方法还有钙盐沉淀法、铁盐沉淀法、硫化沉淀法等[3-7]。用钙盐沉淀法处理砷碱渣,会产生大量的砷钙渣;另一方面,砷酸钙在二氧化碳的作用下发生分解,又将转化为砷酸,不利于环境保护。罗广福采用硫代硫酸钠处理砷碱渣浸出脱锑液[7]。由于采用硫酸或亚硫酸处理碱液,大量的碳酸钠转化成硫酸钠,硫酸钠不仅产值低,而且回收时能耗高;采用石灰乳液处理脱砷液,可以沉淀出硫酸钙,但会产生大量的碱性脱钙液。在采用硫化法处理含砷污水、污酸方面,不少学者进行了大量的研究工作[7-13]。在此,作者进行无污染砷碱渣处理技术工业试验,通过锑精矿、碳酸盐、砷硫化物的回收,以解决锑冶炼中砷碱渣的环境污染问题。

1 基本原理

对于锑碱性精炼中产出的砷碱渣,由于亚锑酸钠、锑酸钠不溶解于水,因此,容易把它们与砷酸钠等可溶性钠盐分离开。二氧化碳与碳酸钠发生反应形成碳酸氢钠,而碳酸氢钠的溶解度远小于碳酸钠的溶解度,因此,向脱锑液中通入二氧化碳气体,可以脱除脱锑液中大部分碳酸钠。向脱碱液中加入硫化钠溶液,在酸性条件下可沉淀出砷的硫化物。向脱砷液中加入过饱和的氢氧化钡溶液,析出硫酸钡沉淀。

有关的化学反应式如下:

CO2+H2O=H2CO3;
Na2CO3+H2CO3=2NaHCO3;
2Na2HAsO4+5Na2S+6H2O=As2S5↓+14NaOH;
2NaOH+H2SO4=Na2SO4+2H2O;
Na2SO4+Ba(OH)2=BaSO4↓+2NaOH。

无污染砷碱渣处理技术包括脱锑、脱碱、脱砷、脱硫酸根4个工序,其工艺流程如图1所示。

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