ZVI还原技术用于地下水污染物的同步修复及评估预测模拟研究
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摘要
零价铁(ZVI)是一种强还原剂，对于地下水污染物去除具有良好的效果。本文在试验过程中，采用化学还原法制备了微米级Pd／Fe双金属，纳米级Fe和纳米级Ni／Fe双金属等催化还原剂，通过TEM、BET-N_2、XRD等表征手段对还原铁粉、纳米级、普通Pd／Fe颗粒和纳米级Pd／Fe等颗粒的形状和大小、比表面积以及纳米级Fe和纳米级Pd／Fe的晶体结构进行了测定。分别选用还原铁粉、纳米级Fe对六价铬去除率进行了系统研究；采用普通Pd／Fe双金属和纳米级Ni／Fe双金属对邻、对硝基氯苯进行了催化还原脱氯研究；然后采用纳米级Ni／Fe对六价铬和对硝基氯苯进行了同步修复研究，得出反应过程中各反应物和生成物的浓度变化规律。考察了不同催化还原剂、钯化率、纳米级Pd／Fe投加量、反应温度、初始pH值以及反应物初始浓度等因素对处理效果和反应速率的影响。通过产物分析结合铬的氧化还原电势E-pH图研究了六价铬的去除机理，通过中间产物和最终产物分析研究了对硝基氯苯的催化还原脱氯的反应机理。最后通过地下水原位修复中试装置，结合中试实验数据和基础试验数据，建立了ZVI修复污染地下水的预测模型。
本文主要结论如下：
1．通过TEM分析得出纯还原铁粉的表面比较光滑、均匀；普通Pd／Fe表面形成了许多白色小突起，这些白色突起构成了表面催化活性位。大多数纳米级Fe和纳米级Ni／Fe颗粒的直径都在100nm以下，但有团聚现象，球状颗粒连接成树枝状。BET-N_2测得还原铁粉，钯／铁(0.005％)，纳米铁的比表面积分别为0.49、0.62、12.4m~2／g。纳米级Fe和普通Pd／Fe的XRD谱图上都出现与Fe的110衍射(d=0.2027nm)相对应的衍射峰，而普通Pd／Fe的XRD谱图上并未出现金属Pd的衍射峰。
2．影响零价铁去除六价铬反应速率的因素有：零价铁投加量、六价铬初始浓度、反应温度和初始pH值、腐殖酸浓度、铜离子浓度、淀粉投加量等。实验结果表明较大的零价铁投加量、较高的反应温度和较低的初始pH值有利于六价铬的去除反应。腐殖酸浓度、铜离子浓度和淀粉投加量则存在一个合适的浓度范围使六价铬的去除反应速率最快。Cr(Ⅵ)去除的表观动力学常数与铁粉的投加量、比表面积呈线性递增关系；随着初始pH值的升高而减缓。
Zero valent iron is a powerfull reductive agent that can remove the groundwater contaminant.The preparation processes of common Pd/ Fe bimetal, nanoscale Fe and Ni/ Fe bimetal were discussed in this thesis. By making use of TEM, BET-N_2 and XRD etc we measured the shade, sizes and ratio area of reduction iron powder, common Pd/Fe and nanoscale Pd/Fe. Meanwhile, the crystal structures of nanoscale Fe and nanoscale Pd/Fe were also investigated. The regular patterns of concentration of reactant and product in reaction processes were studied by using the following methods and techniques: the Cr(VI) wiping off research using both reduction iron powder and nanoscale Fe, the p-NCB catalysis reduction dechloration research using common Pd/Fe bimetal and nanoscale Ni/Fe bimetal, and the synchronous restoration research of Cr(VI) and p-NCB using nanoscale Ni/Fe bimetal. The influences of many factors such as various catalytic reduction agent, palladium rate, adding dose of nanoscale Pd/Fe, reaction temperature, initial pH values and initial reactant concentration on the disposal effect and reaction rates were investigated. The Cr(VI) wiping off mechanism was studied by analyzing the Oxidation-Reduction Reactions potential analysis based on the E-pH diagram, and the mechanism of p-NCB catalysis reduction dechloration was suggested via the analysis of intermediates and products. In combination of the in situ groundwater treatment pilot plant data with the base experiment data we established a prediction model for the ZVI groundwater restoration. The experimental results are given as follows:
1. The TEM analysis indicates that the surface pure Fe is smooth and even, while the surface pure common Pd/Fe exhibits many small white protuberances, which form the surface catalyzed active bits. It is shown that the diameter of most nanoscale Fe and Ni/Fe is less than 100 nms, and that the catalyst granules conjunct each other and exhibit the branch-shape structure. The BET-N_2 measurement shows that the ratio surface area of the iron powder, Pd/Fe iron (0.005%) and nanoscale Fe are 0.49, 0.62 and 12.4 m~2/g respectively. It is demonstrated that the 110 diffraction peak of Fe (d=0.2027 nm) appears in the XRD diagram of nanoscale Fe and common Pd/Fe. However, there exists no Pd diffraction peaks in the XRD diagram of common Pd/Fe.
2. The possible factors, which have influence on the Fe wiping off Cr(VI) reaction rate, are as follows: Fe adding dose, Cr(VI) beginning concentration ,the reaction temperature, the initial pH value, humic acid concentration, copper ion concentration, starch adding dose and so on. Our experiments indicate that the larger Fe adding dose, the higher reaction temperature with the lower initial pH value has positive effect on the Cr(VI) wiping off reaction. The appropriate humic acid concentration, copper ion concentration and starch adding dose can lead to the rapid reaction rate in the Cr(VI) wiping off reaction. In general, the apparent dynamical constants of Cr(VI) wiping off is linear functions of both the Fe adding dose and the
本文主要结论如下：
1．通过TEM分析得出纯还原铁粉的表面比较光滑、均匀；普通Pd／Fe表面形成了许多白色小突起，这些白色突起构成了表面催化活性位。大多数纳米级Fe和纳米级Ni／Fe颗粒的直径都在100nm以下，但有团聚现象，球状颗粒连接成树枝状。BET-N_2测得还原铁粉，钯／铁(0.005％)，纳米铁的比表面积分别为0.49、0.62、12.4m~2／g。纳米级Fe和普通Pd／Fe的XRD谱图上都出现与Fe的110衍射(d=0.2027nm)相对应的衍射峰，而普通Pd／Fe的XRD谱图上并未出现金属Pd的衍射峰。
2．影响零价铁去除六价铬反应速率的因素有：零价铁投加量、六价铬初始浓度、反应温度和初始pH值、腐殖酸浓度、铜离子浓度、淀粉投加量等。实验结果表明较大的零价铁投加量、较高的反应温度和较低的初始pH值有利于六价铬的去除反应。腐殖酸浓度、铜离子浓度和淀粉投加量则存在一个合适的浓度范围使六价铬的去除反应速率最快。Cr(Ⅵ)去除的表观动力学常数与铁粉的投加量、比表面积呈线性递增关系；随着初始pH值的升高而减缓。
Zero valent iron is a powerfull reductive agent that can remove the groundwater contaminant.The preparation processes of common Pd/ Fe bimetal, nanoscale Fe and Ni/ Fe bimetal were discussed in this thesis. By making use of TEM, BET-N_2 and XRD etc we measured the shade, sizes and ratio area of reduction iron powder, common Pd/Fe and nanoscale Pd/Fe. Meanwhile, the crystal structures of nanoscale Fe and nanoscale Pd/Fe were also investigated. The regular patterns of concentration of reactant and product in reaction processes were studied by using the following methods and techniques: the Cr(VI) wiping off research using both reduction iron powder and nanoscale Fe, the p-NCB catalysis reduction dechloration research using common Pd/Fe bimetal and nanoscale Ni/Fe bimetal, and the synchronous restoration research of Cr(VI) and p-NCB using nanoscale Ni/Fe bimetal. The influences of many factors such as various catalytic reduction agent, palladium rate, adding dose of nanoscale Pd/Fe, reaction temperature, initial pH values and initial reactant concentration on the disposal effect and reaction rates were investigated. The Cr(VI) wiping off mechanism was studied by analyzing the Oxidation-Reduction Reactions potential analysis based on the E-pH diagram, and the mechanism of p-NCB catalysis reduction dechloration was suggested via the analysis of intermediates and products. In combination of the in situ groundwater treatment pilot plant data with the base experiment data we established a prediction model for the ZVI groundwater restoration. The experimental results are given as follows:
1. The TEM analysis indicates that the surface pure Fe is smooth and even, while the surface pure common Pd/Fe exhibits many small white protuberances, which form the surface catalyzed active bits. It is shown that the diameter of most nanoscale Fe and Ni/Fe is less than 100 nms, and that the catalyst granules conjunct each other and exhibit the branch-shape structure. The BET-N_2 measurement shows that the ratio surface area of the iron powder, Pd/Fe iron (0.005%) and nanoscale Fe are 0.49, 0.62 and 12.4 m~2/g respectively. It is demonstrated that the 110 diffraction peak of Fe (d=0.2027 nm) appears in the XRD diagram of nanoscale Fe and common Pd/Fe. However, there exists no Pd diffraction peaks in the XRD diagram of common Pd/Fe.
2. The possible factors, which have influence on the Fe wiping off Cr(VI) reaction rate, are as follows: Fe adding dose, Cr(VI) beginning concentration ,the reaction temperature, the initial pH value, humic acid concentration, copper ion concentration, starch adding dose and so on. Our experiments indicate that the larger Fe adding dose, the higher reaction temperature with the lower initial pH value has positive effect on the Cr(VI) wiping off reaction. The appropriate humic acid concentration, copper ion concentration and starch adding dose can lead to the rapid reaction rate in the Cr(VI) wiping off reaction. In general, the apparent dynamical constants of Cr(VI) wiping off is linear functions of both the Fe adding dose and the
引文
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