D0I:10.13374/.issn1001-053x.2011.08.004 第33卷第8期 北京科技大学学报 Vol.33 No.8 2011年8月 Journal of University of Science and Technology Beijing Aug.2011 异化金属还原菌利用发酵制氢废液还原软锰矿 田京雷》冯雅丽)区李浩然》 齐凤杰”唐新华》 1)北京科技大学土木与环境工程学院，北京1000832)中国科学院过程工程研究所生化工程国家重点实验室，北京100190 ☒通信作者，E-mail:ylfengl26@126.com 摘要利用纯二氧化锰在微酸性条件下对异化金属还原菌进行驯化，二氧化锰的颜色由黑色逐渐变浅至白色，X射线衍射 分析表明微生物可有效还原二氧化锰成为碳酸锰：以发酵制氢废液为还原底物，利用异化金属还原菌在不同酸性条件下直接 浸出低品位软锰矿旷，通过单因素实验研究厌氧条件、H值对锰浸出率的影响，并对制氢废液化学需氧量(COD)的去除率及浸 出机理进行研究.结果表明，异化金属还原菌利用发酵制氢废液还原软锰矿，厌氧浸出优于好氧浸出，最佳H值为3.0~ 3.5,浸出时间为3d时，最大浸出率达到98%：用软锰矿对发酵制氢废液在微酸性条件下进行降解，C0D质量浓度为2612g· L时最大去除率达到84%，C0D去除率随软锰矿量的增加而增大. 关键词软锰矿：金属还原菌：异化还原：生物制氢；废液：化学需氧量(COD) 分类号TF803.21 Pyrolusite reduction with dissimilatory metal reducing bacteria in the effluent of bio-hydrogen production TIAN Jing-Hei,FENG Ya-i,LI Hao-ran?,QI Feng-jie,TANG Xin-hua? 1)School of Civil and Environmental Engineering,University of Science and Technology Beijing,Beijing 100083,China 2)Key State Laboratory of Biochemical Engineering,Institute of Process Engineering,Chinese Academy of Science,Beijing 100190,China Corresponding author,E-mail:ylfengl26@126.com ABSTRACT Dissimilatory metal reducing bacteria were domesticated with MnO:in acidic conditions,and then the MnO:color changed from black to white,even colorless.X-ray diffraction analysis indicated that dissimilatory reductive microbes could reduce MnO,effectively after domestication.Manganese leaching from pyrolusite was investigated by using dissimilatory metal reducing bacteria under acid conditions,with the effluent of bio-hydrogen production as a reducing agent.Single-factor experiments were employed to ex- amine the effects of anaerobic conditions and pH values on the leaching rate of Mn.The removal rate of chemical oxygen demand (COD)and the mechanism were also studied.It was shown that dissimilatory metal reducing bacteria reduced pyrolusite using the ef- fluent of fermentative hydrogen production.The leaching rate of manganese under anaerobic conditions was higher than that under aero- bic conditions,and it could reach 98%under the conditions of pH 3.0-3.5 and the leaching time of 3d.For degrading the effluent of bio-hydrogen production under subacid conditions,the COD removal rate could reach 84%when COD in the effluent of bio-hydrogen production was 2612 mgL,and it would be higher with more pyrolusite. KEY WORDS pyrolusite:metal reducing bacteria:dissimilatory reduction:bio-hydrogen production:effluents;chemical oxygen de- mand (COD) 软锰矿作为一种环境矿物材料，近年来受到广 矿4-；有的浸出矿浆固液不易分离，后续处理困 泛关注-习.其中软锰矿浸出工艺是国内外锰矿研 难，如硫酸亚铁.在酸性介质中采用葡萄糖等有 究的重点.关于软锰矿直接还原浸出法，以往的研 机还原剂团，反应条件温和，锰的浸出率在90%以 究主要集中在无机还原剂，但该类还原剂中有的引 上，且不会引入杂质，具有高效、简单的特点，但是有 入杂质较多，后续浸出液净化难度大，如硫铁 机还原剂价格较高 收稿日期：2010-07-30 基金项目：国家自然科学基金资助项目(20876160)：中央高校专项资金资助项目(FRT-TP-09002B)第 33 卷 第 8 期 2011 年 8 月 北京科技大学学报 Journal of University of Science and Technology Beijing Vol． 33 No． 8 Aug． 2011 异化金属还原菌利用发酵制氢废液还原软锰矿 田京雷1) 冯雅丽1)  李浩然2) 齐凤杰1) 唐新华2) 1) 北京科技大学土木与环境工程学院，北京 100083 2) 中国科学院过程工程研究所生化工程国家重点实验室，北京 100190 通信作者，E-mail: ylfeng126@ 126． com 摘 要 利用纯二氧化锰在微酸性条件下对异化金属还原菌进行驯化，二氧化锰的颜色由黑色逐渐变浅至白色，X 射线衍射 分析表明微生物可有效还原二氧化锰成为碳酸锰; 以发酵制氢废液为还原底物，利用异化金属还原菌在不同酸性条件下直接 浸出低品位软锰矿，通过单因素实验研究厌氧条件、pH 值对锰浸出率的影响，并对制氢废液化学需氧量( COD) 的去除率及浸 出机理进行研究． 结果表明，异化金属还原菌利用发酵制氢废液还原软锰矿，厌氧浸出优于好氧浸出，最佳 pH 值为 3. 0 ～ 3. 5，浸出时间为 3 d 时，最大浸出率达到 98% ; 用软锰矿对发酵制氢废液在微酸性条件下进行降解，COD 质量浓度为 2 612 mg· L － 1 时最大去除率达到 84% ，COD 去除率随软锰矿量的增加而增大． 关键词 软锰矿; 金属还原菌; 异化还原; 生物制氢; 废液; 化学需氧量( COD) 分类号 TF803. 21 Pyrolusite reduction with dissimilatory metal reducing bacteria in the effluent of bio-hydrogen production TIAN Jing-lei 1) ，FENG Ya-li 1)  ，LI Hao-ran2) ，QI Feng-jie 1) ，TANG Xin-hua2) 1) School of Civil and Environmental Engineering，University of Science and Technology Beijing，Beijing 100083，China 2) Key State Laboratory of Biochemical Engineering，Institute of Process Engineering，Chinese Academy of Science，Beijing 100190，China Corresponding author，E-mail: ylfeng126@ 126． com ABSTRACT Dissimilatory metal reducing bacteria were domesticated with MnO2 in acidic conditions，and then the MnO2 color changed from black to white，even colorless． X-ray diffraction analysis indicated that dissimilatory reductive microbes could reduce MnO2 effectively after domestication． Manganese leaching from pyrolusite was investigated by using dissimilatory metal reducing bacteria under acid conditions，with the effluent of bio-hydrogen production as a reducing agent． Single-factor experiments were employed to ex￾amine the effects of anaerobic conditions and pH values on the leaching rate of Mn． The removal rate of chemical oxygen demand ( COD) and the mechanism were also studied． It was shown that dissimilatory metal reducing bacteria reduced pyrolusite using the ef￾fluent of fermentative hydrogen production． The leaching rate of manganese under anaerobic conditions was higher than that under aero￾bic conditions，and it could reach 98% under the conditions of pH 3. 0 － 3. 5 and the leaching time of 3 d． For degrading the effluent of bio-hydrogen production under subacid conditions，the COD removal rate could reach 84% when COD in the effluent of bio-hydrogen production was 2 612 mg·L － 1 ，and it would be higher with more pyrolusite． KEY WORDS pyrolusite; metal reducing bacteria; dissimilatory reduction; bio-hydrogen production; effluents; chemical oxygen de￾mand ( COD) 收稿日期: 2010--07--30 基金项目: 国家自然科学基金资助项目( 20876160) ; 中央高校专项资金资助项目( FRT--TP--09--002B) 软锰矿作为一种环境矿物材料，近年来受到广 泛关注［1 － 3］． 其中软锰矿浸出工艺是国内外锰矿研 究的重点． 关于软锰矿直接还原浸出法，以往的研 究主要集中在无机还原剂，但该类还原剂中有的引 入杂 质 较 多，后续浸出液净化难度大，如 硫 铁 矿［4 － 5］; 有的浸出矿浆固液不易分离，后续处理困 难，如硫酸亚铁［6］． 在酸性介质中采用葡萄糖等有 机还原剂［7］，反应条件温和，锰的浸出率在 90% 以 上，且不会引入杂质，具有高效、简单的特点，但是有 机还原剂价格较高． DOI:10.13374/j.issn1001-053x.2011.08.004