D0L:10.13374.issn1001-053x.2013.09.015 第35卷第9期 北京科技大学学报 Vol.35 No.9 2013年9月 Journal of University of Science and Technology Beijing Sep.2013 香菇培养基废料吸附矿山酸性废水中铜离子 林海，曹丽霞☒，陈月芳，董颖博，霍汉鑫，徐丝瑜，高琨，李洋子 北京科技大学土木与环境工程学院，北京100083 ☒通信作者，E-mail:lixia871226@126.com 摘要研究了废水pH值、C+初始浓度、吸附剂投加量、时间及温度对香菇培养基废料吸附C2+的影响，并探讨 了吸附机理.随着pH值的降低，吸附量显著降低：废料吸附Cu+同时符合Langmuir模型和Freundlich模型，最大吸 附量为33.11mgg1:平衡吸附时间为1h,拟二级动力学模型可以很好地描述吸附过程，相关系数为0.9995：吸附剂 最佳投加量为0gL一1：吸附量随着温度的升高显著减少，热力学研究表明，该吸附过程放热，低温宜自发.对吸附前 后的废料进行扫描电镜及Zeta电位分析表明，废料吸附Cu+在低pH值下以物理吸附为主，而在较高pH值下以化 学吸附为主. 关键词矿山酸性废水：生物吸附：铜：吸附机理 分类号X703.1 Adsorption of copper ions from acid mine drainage using spent shi- itake substrate LIN Hai,CAO Li-ria,CHEN Yue-fang,DONG Ying-bo,HUO Han-Tin,XU Si-yu,GAO Kun,LI Yang-zi Civil and Environmental Engineering School,University of Science and Technology Beijing,Beijing 100083,China Corresponding author,E-mail:lixia871226@126.com ABSTRACT The effects of parameters including solution pH value,initial Cu2+concentration,contact time,spent shiitake substrate dosage,and temperature on the adsorption of Cu2+on the spent shiitake substrate were studied,and the adsorption mechanisms were also analyzed.As the initial pH value lowers,the adsorption capacity decreases.The adsorption of Cu2+on the spent shiitake substrate follows well by the Langmuir and Freundlich equilibrium adsorption models.The maximum adsorption capacity of Cu2+is 33.11 mgg-.The equilibrium time is 1 h.The adsorption kinetic data fit the pseudo-second-order model very well with the correlation coefficient of 0.9995.The adsorbent dosage is optimized to 10 g-L1.Raising the temperature leads to an extreme drop of adsorption capacity.Thermodynamic studies indicate that the biosorption process is exothermic and can react spontaneously more easily at lower temperatures. By means of scanning electron microscopy and Zeta potentials,it is found that the adsorption of Cu2+on the spent shiitake substrate is mainly a physical process at lower pH values,while a chemical one at higher pH values. KEY WORDS acid mine drainage;biosorption;copper;adsorption mechanisms 矿山酸性废水是矿山中的硫化矿物在空气、 属离子，而成为全球矿业面临的最严峻的环境问题 水及微生物的作用下，发生一系列物化及生化反 之一A 应而逐步生成的含有大量金属离子，如F2+、 目前，矿山酸性废水的处理方法主要有沉淀、 Cu2+、Mn2+、Zm2+、Cd2+和As3+的黄棕色酸性 离子交换、氧化还原、铁氧体法、膜分离、电化学、 废水.据统计，不少矿山每天会排放数千至数万立 吸附及微生物法等.这些方法在一定程度上能有 方米的废水四，这些酸性废水由于其水质水量波动 效去除重金属离子，但也存在着诸如成本高、化学 大、排放点分散不易控制、pH值低且含有大量重金 药剂消耗量大、能耗高、产生有害泥渣等缺点.近 收稿日期：2012-07-23 基金项目：环保部环保公益性行业科研专项(201209013)第 35 卷 第 9 期 北 京 科 技 大 学 学 报 Vol. 35 No. 9 2013 年 9 月 Journal of University of Science and Technology Beijing Sep. 2013 香菇培养基废料吸附矿山酸性废水中铜离子 林 海，曹丽霞 ，陈月芳，董颖博，霍汉鑫，徐丝瑜，高 琨，李洋子 北京科技大学土木与环境工程学院，北京 100083 通信作者，E-mail: lixia871226@126.com 摘 要 研究了废水 pH 值、Cu2+ 初始浓度、吸附剂投加量、时间及温度对香菇培养基废料吸附 Cu2+ 的影响，并探讨 了吸附机理. 随着 pH 值的降低，吸附量显著降低；废料吸附 Cu2+ 同时符合 Langmuir 模型和 Freundlich 模型，最大吸 附量为 33.11 mg·g −1；平衡吸附时间为 1 h，拟二级动力学模型可以很好地描述吸附过程，相关系数为 0.9995；吸附剂 最佳投加量为 10 g·L −1；吸附量随着温度的升高显著减少，热力学研究表明，该吸附过程放热，低温宜自发. 对吸附前 后的废料进行扫描电镜及 Zeta 电位分析表明，废料吸附 Cu2+ 在低 pH 值下以物理吸附为主，而在较高 pH 值下以化 学吸附为主. 关键词 矿山酸性废水；生物吸附；铜；吸附机理 分类号 X703.1 Adsorption of copper ions from acid mine drainage using spent shi￾itake substrate LIN Hai, CAO Li-xia , CHEN Yue-fang, DONG Ying-bo, HUO Han-xin, XU Si-yu, GAO Kun, LI Yang-zi Civil and Environmental Engineering School, University of Science and Technology Beijing, Beijing 100083, China Corresponding author, E-mail: lixia871226@126.com ABSTRACT The effects of parameters including solution pH value, initial Cu2+ concentration, contact time, spent shiitake substrate dosage, and temperature on the adsorption of Cu2+ on the spent shiitake substrate were studied, and the adsorption mechanisms were also analyzed. As the initial pH value lowers, the adsorption capacity decreases. The adsorption of Cu2+ on the spent shiitake substrate follows well by the Langmuir and Freundlich equilibrium adsorption models. The maximum adsorption capacity of Cu2+ is 33.11 mg·g −1 . The equilibrium time is 1 h. The adsorption kinetic data fit the pseudo-second-order model very well with the correlation coefficient of 0.9995. The adsorbent dosage is optimized to 10 g·L −1 . Raising the temperature leads to an extreme drop of adsorption capacity. Thermodynamic studies indicate that the biosorption process is exothermic and can react spontaneously more easily at lower temperatures. By means of scanning electron microscopy and Zeta potentials, it is found that the adsorption of Cu2+ on the spent shiitake substrate is mainly a physical process at lower pH values, while a chemical one at higher pH values. KEY WORDS acid mine drainage; biosorption; copper; adsorption mechanisms 矿山酸性废水是矿山中的硫化矿物在空气、 水及微生物的作用下，发生一系列物化及生化反 应而逐步生成的含有大量金属离子， 如 Fe2+、 Cu2+、Mn2+、Zn2+、Cd2+ 和 As3+ 的黄棕色酸性 废水. 据统计，不少矿山每天会排放数千至数万立 方米的废水 [1]，这些酸性废水由于其水质水量波动 大、排放点分散不易控制、pH 值低且含有大量重金 属离子，而成为全球矿业面临的最严峻的环境问题 之一 [2] . 目前，矿山酸性废水的处理方法主要有沉淀、 离子交换、氧化还原、铁氧体法、膜分离、电化学、 吸附及微生物法等. 这些方法在一定程度上能有 效去除重金属离子，但也存在着诸如成本高、化学 药剂消耗量大、能耗高、产生有害泥渣等缺点. 近 收稿日期：2012-07-23 基金项目：环保部环保公益性行业科研专项 (201209013) DOI:10.13374/j.issn1001-053x.2013.09.015