纳米Fe/Ni双金属颗粒的制备优化及其去除水中CAHs的基础研究
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摘要
氯代脂肪烃(Chlorinated Aliphatic Hydrocarbons-CAHs)作为化工原料和有机溶剂被广泛的应用于化工、制革、医药和电子等行业,使用过程中发生的泄漏、喷射以及工业的直接排放,引起土壤和地下水的CAHs污染。本文旨在研究纳米零价铁和镍组成的双金属体系对CAHs的还原脱氯作用,从而达到治理地下水污染的目的。使用液相化学还原共沉淀法制备纳米Fe/Ni双金属颗粒时,添加42%聚乙二醇作为分散剂,选择冷冻干燥作为干燥方法,可以得到性能较优良的纳米双金属颗粒材料。纳米Fe/Ni颗粒粒径较小(约为20nnm),呈现非晶态纳米合金结构。通过使用不同Ni含量纳米Fe/Ni颗粒对于三种不同CAHs进行批式降解实验,发现对于PCE和1,1,1-TCA的还原降解而言,最佳Ni含量为11%；而对于TCE最佳Ni含量为6%,这证明并非催化金属Ni的含量越高,其对CAHs的降解效能就越好。随着投加量的增大,纳米Fe/Ni颗粒对TCE降解速率和去除率随之增加。在1,1,1-TCA和TCE共存于水相时,其降解效能和速率相较于单独降解过程都有不同程度的下降。Ca2+、Mg2+、Na+、SO42-、NO3-、Cl和甲醇对于1,1,1-TCA和TCE的降解过程均表现出抑制作用,而腐殖酸钠对于CAHs降解的影响是竞争吸附和传递电子两方面作用的叠加。纳米Fe/Ni对于CAHs的去除动力学符合伪-级反应动力学模型。
Chlorinated aliphatic hydrocarbons (CAHs) as chemical raw materials and organic solvents, are widely used in chemical, leather, pharmaceutical and electronics industries. As a result of the leakage or injetion occur in the process and industrial direct emissions, CAHs results in the critical contamination of soil and groundwater environments. The objective of this study is to evaluate the effectiveness of removing CAHs from groundwater with nano-scale Fe/Ni (iron/nickel) particles. Liquid phase chemical reduction coprecipitation method, chosen 42% polyethylene glycol as dispersing agent and freeze drying as the dring technique, was employed for the preparation of nano-Fe/Ni bimetallic materials. The Fe/Ni particles, with average size of 20nm, have amorphous nano-alloy structure. The results of batch CAHs degradation experiments by nano Fe/Ni with different Ni content shown that, for 1,1,1-TCA and PCE, the optimum Ni content is 11%, while nano Fe/Ni with 6% Ni content has the best removal capacity for TCE. This phenomenon implies that the higher content of Ni metal catalyst doesn't mean the better performance for CAHs removal. As the dosage increases, the nano-Fe/Ni particles will reduce TCE more quickly with higher removal rate. When 1,1,1-TCA and TCE co-exist in the water, slower reduction was observed with lower removal rate for each CAH. Ca2+, Mg+, Na+,SO42-,NO3-, Cl-, and methanol were found have negative effects on 1,1,1-TCA and TCE degradation, while the effect of humic acid sodium is constituted of competitive adsorption and transmission of electron. The CAHs removal kinetics by nano Fe/Ni consists with the pseudo-first order kinetics model.
Chlorinated aliphatic hydrocarbons (CAHs) as chemical raw materials and organic solvents, are widely used in chemical, leather, pharmaceutical and electronics industries. As a result of the leakage or injetion occur in the process and industrial direct emissions, CAHs results in the critical contamination of soil and groundwater environments. The objective of this study is to evaluate the effectiveness of removing CAHs from groundwater with nano-scale Fe/Ni (iron/nickel) particles. Liquid phase chemical reduction coprecipitation method, chosen 42% polyethylene glycol as dispersing agent and freeze drying as the dring technique, was employed for the preparation of nano-Fe/Ni bimetallic materials. The Fe/Ni particles, with average size of 20nm, have amorphous nano-alloy structure. The results of batch CAHs degradation experiments by nano Fe/Ni with different Ni content shown that, for 1,1,1-TCA and PCE, the optimum Ni content is 11%, while nano Fe/Ni with 6% Ni content has the best removal capacity for TCE. This phenomenon implies that the higher content of Ni metal catalyst doesn't mean the better performance for CAHs removal. As the dosage increases, the nano-Fe/Ni particles will reduce TCE more quickly with higher removal rate. When 1,1,1-TCA and TCE co-exist in the water, slower reduction was observed with lower removal rate for each CAH. Ca2+, Mg+, Na+,SO42-,NO3-, Cl-, and methanol were found have negative effects on 1,1,1-TCA and TCE degradation, while the effect of humic acid sodium is constituted of competitive adsorption and transmission of electron. The CAHs removal kinetics by nano Fe/Ni consists with the pseudo-first order kinetics model.
引文
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[5]张国俊,孟洪,薛峰TCE/PCE的DNAPL污染及零价铁墙防治技术[J].环境污染防治技术与设备,2006,7(4)：12-18.
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