Xu Wen-Ying, Gao Ting-Yao
The National Engineering Research Center for Urban Pollution Control, Tongji University, Shanghai 200092, China.
J Environ Sci (China). 2007;19(7):792-9. doi: 10.1016/s1001-0742(07)60133-8.
The electrochemical reduction characteristics of carbon tetrachloride (CT) were investigated using cyclic voltammetry in this study. In addition, the difference in reduction mechanisms of CT between Master Builders' iron and the catalyzed Fe-Cu process was discussed. The results showed that CT was reduced directly on the surface of copper rather than by atomic hydrogen produced at the cathode in the catalyzed Fe-Cu process. The reduction was realized largely by atomic hydrogen in Master Builders' iron. The entire CT in 350 ml aqueous solution with 320 mg/L was reduced to trichloromethane and dichloromethane in 2.25 h when 100 g of scrap iron with Fe/Cu ratio of 10:1 (w/w) were used. Moreover, the reduction rate slowed with time. CT could be reduced at acidic, neutral and alkaline pH from solution by Fe-Cu bimetallic media, but the mechanisms were different. The degradation rate was not significantly influenced by pH in the catalyzed Fe-Cu process; in Master Builders' iron it clearly increased with decreasing pH. The kinetics of the reductions followed pseudo-first order in both cases. Furthermore, the reductions under acidic conditions proceeded faster than that under the neutral and alkaline conditions. The catalyzed Fe-Cu process was superior to Master Builders' iron in treating CT-containing water and this advantage was particularly noticeable under alkaline conditions. The reduction was investigated in the cathode (Cu) and anode (Fe) compartments respectively, the results showed that the direct reduction pathway played an important role in the reduction by the catalyzed Fe-Cu process. The catalyzed Fe-Cu process is of practical value.
本研究采用循环伏安法研究了四氯化碳(CT)的电化学还原特性。此外,还讨论了万能工匠铁与催化铁 - 铜工艺中CT还原机制的差异。结果表明,在催化铁 - 铜工艺中,CT是直接在铜表面还原,而非通过阴极产生的原子氢还原。在万能工匠铁中,还原主要通过原子氢实现。当使用100 g铁铜比为10:1(w/w)的废铁时,350 ml含320 mg/L CT的水溶液中的全部CT在2.25 h内被还原为三氯甲烷和二氯甲烷。此外,还原速率随时间减慢。铁 - 铜双金属介质可在酸性、中性和碱性pH条件下还原溶液中的CT,但机制不同。在催化铁 - 铜工艺中,降解速率不受pH的显著影响;在万能工匠铁中,降解速率明显随pH降低而增加。两种情况下还原动力学均遵循准一级反应。此外,酸性条件下的还原比中性和碱性条件下更快。在处理含CT的水方面,催化铁 - 铜工艺优于万能工匠铁,且在碱性条件下这一优势尤为明显。分别在阴极(Cu)和阳极(Fe)隔室中研究了还原过程,结果表明直接还原途径在催化铁 - 铜工艺的还原中起重要作用。催化铁 - 铜工艺具有实际应用价值。