工程科学学报，第39卷，第3期：383-388,2017年3月 Chinese Journal of Engineering,Vol.39,No.3:383-388,March 2017 DOI:10.13374/j.issn2095-9389.2017.03.010:http://journals.ustb.edu.cn 次亚磷酸盐在电解铜氰废液同时回收铜和氰过程中 的作用 高腾跃”，刘奎仁)区，韩庆”，徐滨士) 1)东北大学治金学院，沈阳1108192)装甲兵工程学院装备再制造技术国防重点实验室，北京100072 ☒通信作者，E-mail:liukr(@smm.ncu.cdu.cn 摘要以高浓度铜氰溶液为研究对象，通过添加次亚磷酸盐，进行了高碱条件下电积回收铜与氰化物的研究.研究了次亚 磷酸盐用量、温度对铜和氰化物沉积过程的影响：利用线性循环伏安、恒电位电解并结合X射线衍射分析阳极沉淀物的物相， 分析了阳极反应机理和次亚磷酸盐抑制氰化物分解的机理：采用电解后余液进行金的氰化浸出实验.结果表明：次亚磷酸盐 可有效抑制电沉积过程中氰化物的分解，其抑制效果随温度升高而增强.电解过程中阳极表面生成的C2·是造成氰化物分 解的主要原因：次亚磷酸盐通过优先与C·发生氧化还原反应从而抑制氰化物的分解.处理后余液对金的氰化浸出无不良 影响，通过电解可综合回收铜氰废水中金属与氰化物，处理后废水可循环利用. 关键词废水处理：次亚磷酸盐；电沉积：回收 分类号TF803.27 Effect of hypophosphite during the recovery of copper and cyanide from high concentration copper-cyanide wastewater by electrodeposition GA0 Teng-yue》,IUKi+en》,HAN Qing》,XU Bin-shi2 1)School of Metallurgy,Northeastern University,Shenyang 110819,China 2)National Key Laboratory for Remanufacturing,Academy of Armored Forces Engineering,Beijing 100072,China Corresponding author,E-mail:liukr@smm.neu.edu.cn ABSTRACT The recovery of copper and cyanide from high concentration wastewater was conducted by electrodeposition with high basicity.The effect of hypophosphite dosage and temperature on recycling copper and cyanide from wastewater was investigated.The linear cyclic voltammetry,potentiostatic electrolysis and X-ray diffraction analysis were used to research the anodic reaction and pre- cipitate phase,the mechanisms of cyanide decomposition and hypophosphite inhibition were also analyzed.The experiment of cyanide leaching of gold was done in residual liquid after electrolysis.The results indicate that the damage of cyanide is effectively suppressed by hypophosphite.The inhibitory effect is enhanced gradually with increasing temperature.The Cuforming on the anode surface is the main reason to degrade cyanide.Hypophosphite restrains cyanide from degradation by preferential oxidation.The tail liquid has no effect on leaching of gold,and the copper-cyanide wastewater can be comprehensively recovered the valuable metals and cyanide by electrodeposition. KEY WORDS wastewater treatment:hypophosphite;electrodeposition:recovery 采用氰化浸出工艺处理含铜金矿时会产生大量含用四.由于黄金矿山含氰废水量较大，使得采用传统 铜含氰废水.氰化液中铜的存在会增加氰耗，同时降 净化法回处理时存在药剂消耗大、生产成本高等问题： 低金的浸出速度，因而含铜含氧废水无法直接循环使 并且废水中的有价金属和氰化物无法实现回收，造成 收稿日期：201605-28工程科学学报，第 39 卷，第 3 期: 383--388，2017 年 3 月 Chinese Journal of Engineering，Vol． 39，No． 3: 383--388，March 2017 DOI: 10． 13374 /j． issn2095--9389． 2017． 03． 010; http: / /journals． ustb． edu． cn 次亚磷酸盐在电解铜氰废液同时回收铜和氰过程中 的作用 高腾跃1) ，刘奎仁1) ，韩 庆1) ，徐滨士2) 1) 东北大学冶金学院，沈阳 110819 2) 装甲兵工程学院装备再制造技术国防重点实验室，北京 100072 通信作者，E-mail: liukr@ smm． neu． edu． cn 摘 要 以高浓度铜氰溶液为研究对象，通过添加次亚磷酸盐，进行了高碱条件下电积回收铜与氰化物的研究． 研究了次亚 磷酸盐用量、温度对铜和氰化物沉积过程的影响; 利用线性循环伏安、恒电位电解并结合 X 射线衍射分析阳极沉淀物的物相， 分析了阳极反应机理和次亚磷酸盐抑制氰化物分解的机理; 采用电解后余液进行金的氰化浸出实验． 结果表明: 次亚磷酸盐 可有效抑制电沉积过程中氰化物的分解，其抑制效果随温度升高而增强． 电解过程中阳极表面生成的 Cu2 + 是造成氰化物分 解的主要原因; 次亚磷酸盐通过优先与 Cu2 + 发生氧化还原反应从而抑制氰化物的分解． 处理后余液对金的氰化浸出无不良 影响，通过电解可综合回收铜氰废水中金属与氰化物，处理后废水可循环利用． 关键词 废水处理; 次亚磷酸盐; 电沉积; 回收 分类号 TF803. 27 Effect of hypophosphite during the recovery of copper and cyanide from high concentration copper--cyanide wastewater by electrodeposition GAO Teng-yue1) ，LIU Kui-ren1)  ，HAN Qing1) ，XU Bin-shi2) 1) School of Metallurgy，Northeastern University，Shenyang 110819，China 2) National Key Laboratory for Ｒemanufacturing，Academy of Armored Forces Engineering，Beijing 100072，China Corresponding author，E-mail: liukr@ smm． neu． edu． cn ABSTＲACT The recovery of copper and cyanide from high concentration wastewater was conducted by electrodeposition with high basicity． The effect of hypophosphite dosage and temperature on recycling copper and cyanide from wastewater was investigated． The linear cyclic voltammetry，potentiostatic electrolysis and X-ray diffraction analysis were used to research the anodic reaction and pre￾cipitate phase，the mechanisms of cyanide decomposition and hypophosphite inhibition were also analyzed． The experiment of cyanide leaching of gold was done in residual liquid after electrolysis． The results indicate that the damage of cyanide is effectively suppressed by hypophosphite． The inhibitory effect is enhanced gradually with increasing temperature． The Cu2 + forming on the anode surface is the main reason to degrade cyanide． Hypophosphite restrains cyanide from degradation by preferential oxidation． The tail liquid has no effect on leaching of gold，and the copper--cyanide wastewater can be comprehensively recovered the valuable metals and cyanide by electrodeposition． KEY WOＲDS wastewater treatment; hypophosphite; electrodeposition; recovery 收稿日期: 2016--05--28 采用氰化浸出工艺处理含铜金矿时会产生大量含 铜含氰废水． 氰化液中铜的存在会增加氰耗，同时降 低金的浸出速度，因而含铜含氰废水无法直接循环使 用［1］． 由于黄金矿山含氰废水量较大，使得采用传统 净化法［2］处理时存在药剂消耗大、生产成本高等问题; 并且废水中的有价金属和氰化物无法实现回收，造成