工程科学学报，第41卷，第5期：591-599.2019年5月 Chinese Journal of Engineering,Vol.41,No.5:591-599,May 2019 DOI:10.13374/j.issn2095-9389.2019.05.005;http://journals.ustb.edu.cn Acidithiobacillus ferrooxidans对软锰矿浸出的影响 康金星)，冯雅丽)四，李浩然)，杜竹玮)，邓祥意”，王洪君) 1)北京科技大学土木与资源工程学院，北京1000832)中国科学院过程工程研究所，北京100190 ☒通信作者，E-mail:ylfengl26@126.com 摘要利用循环伏安、交流阻抗谱和极化曲线研究了Acidithiobacillus ferrooxidans对软锰矿在模拟浸出溶液(9K基础培养 基，A.ferrooxidans,Fe(Ⅲ)，A.ferrooxidans+Fe(Ⅲ)）中电化学腐蚀行为的影响：利用模拟有菌/无菌浸出溶液中钝化膜的 Mott-Schottky理论比较了有无细菌存在情况下形成的钝化膜的优劣性.结果表明，A.ferrooxidans促进MnO,/Mn2+氧化还原转 化，催化MnO,/Mn(OH),电极反应：加速软锰矿/溶液界面电子交换，无铁存在时A.ferrooxidans使电荷转移内阻降低34%，比 含Fe(Ⅲ)无菌体系低11%：引起软锰矿电极极化，增强其氧化活性：加速MnO,向Mn0.OH转化及其产物扩散.A.ferrooxidans 与软锰矿作用更倾向于间接作用机理.在选取的各模拟电解液(H值为2.0)中，0.2~0.4V区间内软锰矿形成耗尽层，在 模拟浸出溶液中形成的饨化膜都表现出p~n~p~n型半导体性能.在选取的0.2V极化电位下，无铁时引人A.ferrooxidans使膜 中的施主/受主密度减少，细菌含有多种基团参与半导体/溶液界面电子转移反应，接受界面间自由电子或填充空穴，促使软 锰矿与溶液界面物质交换变频繁：含铁溶液中加入A.ferrooxidans使得钝化膜受主/施主密度增大，A.ferrooxidans降低了膜的 耐腐蚀性，因而促进软锰矿浸出 关键词软锰矿；Acidithiobacillus ferrooxidans;浸出；电化学腐蚀；电荷转移；半导体 分类号TF111.311 Effect of Acidithiobacillus ferrooxidans on pyrolusite bioleaching KANG Jin-xing,FENG Ya-li),LI Hao-ran2),DU Zhu-wei2),DENG Xiang-yi),WANG Hong-jun') 1)School of Civil and Resource Engineering.University of Science and Technology Beijing.Beijing 100083.China 2)Institute of Process Engineering,Chinese Academy of Sciences,Beijing 100190,China Corresponding author,E-mail:ylfengl26@126.com ABSTRACT Biohydrometallurgy is an increasingly popular ore extraction technology and is especially applicable for low-grade ores. In particular,Acidithiobacillus ferrooxidans (A.ferrooxidans)is by far the most widely used bioleaching microorganism for leaching ores,including for sulfide ores and manganese dioxide ores.At present,many works are focused on the vital facilitating role of A.fer- rooxidans in the cycles of sulfur and iron for sulfide ores bioleaching.However,research on the effect of A.ferrooxidans on manganese dioxide ores leaching is limited.The effects of A.ferrooxidans on the electrochemistry behavior of pyrolusite in simulated solutions (9K basic medium,A.ferrooxidans,Fe(Il),A.ferrooxidans +Fe(Il))were investigated using cyclic voltammetry,electrochemical impedance spectroscopy (EIS),and potentiodynamic polarization.Mott-Schottky curves were utilized to determine the passive film formed on the surface of pyrolusite ore in the presence or absence of bacteria bath solutions.The results show that A.ferrooxidans pro- motes the redox of MnO/Mn2 and triggers the reaction of MnO2/Mn(OH)2.A.ferrooxidans accelerates electron exchange between pyrolusite and solution;in the A.ferrooxidans-simulated solution,the charge-transfer reaction resistance of manganese dioxide is 34% lower than that of the control (9K)and 11%lower than that of the Fe(I)solution.Germs cause polarization of pyrolusite,leading to 收稿日期：2018-04-12 基金项目：国家自然科学基金资助项目(20176026,20176242)；国家水体污染控制与治理科技重大专项资助项目(2015ZX07205-003):中国大 洋矿产资源研究计划资助项目(DY125-15-T08)工程科学学报,第 41 卷,第 5 期:591鄄鄄599,2019 年 5 月 Chinese Journal of Engineering, Vol. 41, No. 5: 591鄄鄄599, May 2019 DOI: 10. 13374 / j. issn2095鄄鄄9389. 2019. 05. 005; http: / / journals. ustb. edu. cn Acidithiobacillus ferrooxidans 对软锰矿浸出的影响 康金星1) , 冯雅丽1)苣 , 李浩然2) , 杜竹玮2) , 邓祥意1) , 王洪君1) 1) 北京科技大学土木与资源工程学院, 北京 100083 2) 中国科学院过程工程研究所, 北京 100190 苣通信作者, E鄄mail: ylfeng126@ 126. com 摘 要 利用循环伏安、交流阻抗谱和极化曲线研究了 Acidithiobacillus ferrooxidans 对软锰矿在模拟浸出溶液(9K 基础培养 基, A. ferrooxidans,Fe(芋), A. ferrooxidans + Fe(芋) )中电化学腐蚀行为的影响;利用模拟有菌/ 无菌浸出溶液中钝化膜的 Mott鄄鄄Schottky 理论比较了有无细菌存在情况下形成的钝化膜的优劣性. 结果表明,A. ferrooxidans 促进 MnO2 / Mn 2 + 氧化还原转 化,催化 MnO2 / Mn(OH)2电极反应;加速软锰矿/ 溶液界面电子交换,无铁存在时 A. ferrooxidans 使电荷转移内阻降低 34% ,比 含 Fe(芋)无菌体系低 11% ;引起软锰矿电极极化,增强其氧化活性;加速 MnO2向 MnO·OH 转化及其产物扩散. A. ferrooxidans 与软锰矿作用更倾向于间接作用机理. 在选取的各模拟电解液 (pH 值为 2郾 0) 中,0郾 2 ~ 0郾 4 V 区间内软锰矿形成耗尽层,在 模拟浸出溶液中形成的钝化膜都表现出 p鄄鄄n鄄鄄p鄄鄄n 型半导体性能. 在选取的 0郾 2 V 极化电位下,无铁时引入 A. ferrooxidans 使膜 中的施主/ 受主密度减少,细菌含有多种基团参与半导体/ 溶液界面电子转移反应,接受界面间自由电子或填充空穴,促使软 锰矿与溶液界面物质交换变频繁;含铁溶液中加入 A. ferrooxidans 使得钝化膜受主/ 施主密度增大,A. ferrooxidans 降低了膜的 耐腐蚀性,因而促进软锰矿浸出. 关键词 软锰矿; Acidithiobacillus ferrooxidans; 浸出; 电化学腐蚀; 电荷转移; 半导体 分类号 TF111郾 311 收稿日期: 2018鄄鄄04鄄鄄12 基金项目: 国家自然科学基金资助项目(20176026,20176242); 国家水体污染控制与治理科技重大专项资助项目(2015ZX07205鄄003); 中国大 洋矿产资源研究计划资助项目(DY125鄄15鄄T鄄08) Effect of Acidithiobacillus ferrooxidans on pyrolusite bioleaching KANG Jin鄄xing 1) , FENG Ya鄄li 1) 苣 , LI Hao鄄ran 2) , DU Zhu鄄wei 2) , DENG Xiang鄄yi 1) , WANG Hong鄄jun 1) 1) School of Civil and Resource Engineering, University of Science and Technology Beijing, Beijing 100083, China 2) Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China 苣Corresponding author, E鄄mail: ylfeng126@ 126. com ABSTRACT Biohydrometallurgy is an increasingly popular ore extraction technology and is especially applicable for low鄄grade ores. In particular, Acidithiobacillus ferrooxidans (A. ferrooxidans) is by far the most widely used bioleaching microorganism for leaching ores, including for sulfide ores and manganese dioxide ores. At present, many works are focused on the vital facilitating role of A. fer鄄 rooxidans in the cycles of sulfur and iron for sulfide ores bioleaching. However, research on the effect of A. ferrooxidans on manganese dioxide ores leaching is limited. The effects of A. ferrooxidans on the electrochemistry behavior of pyrolusite in simulated solutions (9K basic medium, A. ferrooxidans, Fe(芋), A. ferrooxidans + Fe(芋)) were investigated using cyclic voltammetry, electrochemical impedance spectroscopy (EIS), and potentiodynamic polarization. Mott鄄鄄 Schottky curves were utilized to determine the passive film formed on the surface of pyrolusite ore in the presence or absence of bacteria bath solutions. The results show that A. ferrooxidans pro鄄 motes the redox of MnO2 / Mn 2 + and triggers the reaction of MnO2 / Mn(OH)2 . A. ferrooxidans accelerates electron exchange between pyrolusite and solution; in the A. ferrooxidans鄄simulated solution, the charge鄄transfer reaction resistance of manganese dioxide is 34% lower than that of the control (9K) and 11% lower than that of the Fe(芋) solution. Germs cause polarization of pyrolusite, leading to