趋磁细菌对贵金属离子的选择性吸附行为及溶液中金的回收研究
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摘要
随着高新技术的迅猛发展,全世界对贵重金属的需求量越来越大,但其储量却十分有限。因此,含贵重金属废料的资源化和循环利用技术已成为国内外相关人士关注的焦点。本文对“选择吸附-高梯度磁分离”耦合工艺回收废水中金和铜的过程进行了系统的理论分析与实验研究。
本文从污水处理厂活性污泥中筛选到一株趋磁性较强且对金属离子有较高吸附能力的菌株MTB-3,根据生理生化实验和16S rDNA测序结果,确定出该菌种为Stenotrophomonas sp.细菌,是该属一个具有趋磁特性的新菌种。
实验确定了Stenotrophomonas sp. MTB-3在单元体系中对Au~(3+)、Cu~(2+)和Ni~(2+)的最佳吸附条件,进而考察了该菌在Au~(3+)-Cu~(2+)二元体系及Au~(3+)-Cu~(2+)-Ni~(2+)三元体系中的吸附特性,并通过等温吸附特性及吸附动力学特性研究获得相应的吸附参数,结果表明菌体对多元体系中的Au~(3+)具有优先选择吸附的能力。对菌体上金的脱附研究发现,0.8mol/L的硫脲对金的脱附率可达91.3%;在保证菌体再吸附率高于80%的前提下,菌体至少可以重复使用三次。
以透射电镜(TEM)、傅立叶变换红外光谱仪(FTIR)、X射线衍射仪(XRD)、光电子能谱仪(XPS)等先进仪器为实验分析手段,并结合理论模型探讨了Stenotrophomonas sp. MTB-3对Au~(3+)、Cu~(2+)和Ni~(2+)的吸附机理,研究发现该菌吸附Cu~(2+)、Ni~(2+)的主要机理是静电引力和表面络合作用;而吸附Au~(3+)的主要机理是静电引力、表面络合作用及氧化还原作用。在此基础上得出MTB-3菌体吸附贵重金属离子的微观过程初步模型。
通过对颗粒在磁场中受力和力矩作用分析,推导并建立了高梯度磁分离过程中菌体微粒在轴向饱和堆积的物理模型和数学模型,用以描述菌体微粒沿金属丝轴线方向运动时被捕集并堆积的情况;并采用现象学磁分离模型,描述并预测吸附贵重金属离子后的菌体在整个磁分离空间内被捕集的动力学特性。
基于MTB-3菌较强的趋磁特性以及在多元体系中对Au~(3+)的可调节选择吸附能力,开发了“选择吸附-高梯度磁分离”耦合工艺,该工艺对于Au~(3+)-Cu~(2+)二元体系中金和铜的回收率可分别达到90.2%和81.0%,而且处理后的水满足国家对废水中Au~(3+)和Cu~(2+)的废水排放标准。
With the rapid development of novel technologies in industries,the demand of precious metal in the world is increasing. However, due to the limited reserves of precious metal, the recovery technology from precious metal contained wastes has drawn more attention recently. Therefore, the aim in the present study is to investigate the feasibility of applying the coupling technology, selective biosorption and HGMS (high gradient magnetic separation), into the gold recovery from industrial wastewater.
A magnetotactic bacterial isolate (MTB-3) with a high biosorption capacity to metal ions was isolated and purified from the Jizhuangzi sewage treatment plant. By means of series of the physiological biochemical experiments and the 16S rDNA sequence analysis, this strain was identified as Stenotrophomonas sp.
The optimal biosorption conditions of Stenotrophomonas sp. MTB-3 to Au(III), Cu(II) and Ni(II) in single, binary and ternary systems were investigated, and the results of kinetic and equilibrium studies indicated that MTB-3 showed a high selectivity to Au(III) in multi-systems. The results of the desorption experiments suggested that 91.3% Au adsorbed on the biomass could be recovered when the thiourea concentration was 0.8 M, and the biomass could be used more than three times with an essential prerequisite that the re-biosorption ratio was more than 80%.
The biosorption mechanisms of MTB-3 in the removal of Au(III), Cu(II) and Ni(II) were investigated using theory models, combined with the chemical analysis, such as Transmission electron microscope (TEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and chemical modification experiments. The results indicated that the static attraction and surface complexation reactions were the main mechanisms as for the biosorption of Cu(II) and Ni(II), while adsorption together with bioreduction were the dominant mechanisms as for Au(III). The preliminary microcosmic model of biosorption of metal ions by MTB-3 was then developed on the basis of biosorption mechanisms.
After analyzing the force and their moment acting on the metal loaded MTB-3 in the magnetic field, the axial saturation build-up model was established to describe the performance of the MTB-3 cells in the HGMS process. Combined with the phenomenology model, kinetic characteristic of the movement of the metal loaded cells in the whole magnetic separator was described and predicted.
Based on the high magnetotaxis and the high selective biosorption capacity of Stenotrophomonas sp. biomass, a coupling technology“selective biosorption and HGMS”was put forward in this study to recover gold from wastewater. The results showed that the recovery ratio for gold and copper were 90.2% and 81.0%, respectively, and the discharged water could meet the national drainage standard for gold(III) and copper(II).
本文从污水处理厂活性污泥中筛选到一株趋磁性较强且对金属离子有较高吸附能力的菌株MTB-3,根据生理生化实验和16S rDNA测序结果,确定出该菌种为Stenotrophomonas sp.细菌,是该属一个具有趋磁特性的新菌种。
实验确定了Stenotrophomonas sp. MTB-3在单元体系中对Au~(3+)、Cu~(2+)和Ni~(2+)的最佳吸附条件,进而考察了该菌在Au~(3+)-Cu~(2+)二元体系及Au~(3+)-Cu~(2+)-Ni~(2+)三元体系中的吸附特性,并通过等温吸附特性及吸附动力学特性研究获得相应的吸附参数,结果表明菌体对多元体系中的Au~(3+)具有优先选择吸附的能力。对菌体上金的脱附研究发现,0.8mol/L的硫脲对金的脱附率可达91.3%;在保证菌体再吸附率高于80%的前提下,菌体至少可以重复使用三次。
以透射电镜(TEM)、傅立叶变换红外光谱仪(FTIR)、X射线衍射仪(XRD)、光电子能谱仪(XPS)等先进仪器为实验分析手段,并结合理论模型探讨了Stenotrophomonas sp. MTB-3对Au~(3+)、Cu~(2+)和Ni~(2+)的吸附机理,研究发现该菌吸附Cu~(2+)、Ni~(2+)的主要机理是静电引力和表面络合作用;而吸附Au~(3+)的主要机理是静电引力、表面络合作用及氧化还原作用。在此基础上得出MTB-3菌体吸附贵重金属离子的微观过程初步模型。
通过对颗粒在磁场中受力和力矩作用分析,推导并建立了高梯度磁分离过程中菌体微粒在轴向饱和堆积的物理模型和数学模型,用以描述菌体微粒沿金属丝轴线方向运动时被捕集并堆积的情况;并采用现象学磁分离模型,描述并预测吸附贵重金属离子后的菌体在整个磁分离空间内被捕集的动力学特性。
基于MTB-3菌较强的趋磁特性以及在多元体系中对Au~(3+)的可调节选择吸附能力,开发了“选择吸附-高梯度磁分离”耦合工艺,该工艺对于Au~(3+)-Cu~(2+)二元体系中金和铜的回收率可分别达到90.2%和81.0%,而且处理后的水满足国家对废水中Au~(3+)和Cu~(2+)的废水排放标准。
With the rapid development of novel technologies in industries,the demand of precious metal in the world is increasing. However, due to the limited reserves of precious metal, the recovery technology from precious metal contained wastes has drawn more attention recently. Therefore, the aim in the present study is to investigate the feasibility of applying the coupling technology, selective biosorption and HGMS (high gradient magnetic separation), into the gold recovery from industrial wastewater.
A magnetotactic bacterial isolate (MTB-3) with a high biosorption capacity to metal ions was isolated and purified from the Jizhuangzi sewage treatment plant. By means of series of the physiological biochemical experiments and the 16S rDNA sequence analysis, this strain was identified as Stenotrophomonas sp.
The optimal biosorption conditions of Stenotrophomonas sp. MTB-3 to Au(III), Cu(II) and Ni(II) in single, binary and ternary systems were investigated, and the results of kinetic and equilibrium studies indicated that MTB-3 showed a high selectivity to Au(III) in multi-systems. The results of the desorption experiments suggested that 91.3% Au adsorbed on the biomass could be recovered when the thiourea concentration was 0.8 M, and the biomass could be used more than three times with an essential prerequisite that the re-biosorption ratio was more than 80%.
The biosorption mechanisms of MTB-3 in the removal of Au(III), Cu(II) and Ni(II) were investigated using theory models, combined with the chemical analysis, such as Transmission electron microscope (TEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and chemical modification experiments. The results indicated that the static attraction and surface complexation reactions were the main mechanisms as for the biosorption of Cu(II) and Ni(II), while adsorption together with bioreduction were the dominant mechanisms as for Au(III). The preliminary microcosmic model of biosorption of metal ions by MTB-3 was then developed on the basis of biosorption mechanisms.
After analyzing the force and their moment acting on the metal loaded MTB-3 in the magnetic field, the axial saturation build-up model was established to describe the performance of the MTB-3 cells in the HGMS process. Combined with the phenomenology model, kinetic characteristic of the movement of the metal loaded cells in the whole magnetic separator was described and predicted.
Based on the high magnetotaxis and the high selective biosorption capacity of Stenotrophomonas sp. biomass, a coupling technology“selective biosorption and HGMS”was put forward in this study to recover gold from wastewater. The results showed that the recovery ratio for gold and copper were 90.2% and 81.0%, respectively, and the discharged water could meet the national drainage standard for gold(III) and copper(II).
引文
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