铜类芬顿反应对电镀废水中有机物降解的研究

发布时间：2018-04-14 11:05

本文选题：铜类-Fenton反应 + 电镀废水　；参考：《南昌航空大学》2016年硕士论文

【摘要】：电镀铜废水中含有大量的有机污染物和金属铜离子,铜离子作为3d轨道过渡金属离子具有类似于铁离子的性质,也可以催化分解过氧化氢产生高氧化性能的活性物质。本研究以占电镀废水20%的镀铜工业废水为模拟研究对象,利用电镀废水中本身存在的金属铜离子为催化剂,加入绿色、高效、廉价易得、对环境影响小的过氧化氢作为氧化剂,利用其反应过程中产生的高氧化性能的活性物质降解有机底物,不仅节约了成本,更为后续金属离子的回用处理消除了有机物的干扰。本论文在单纯铜类芬顿体系的基础上,研究了过渡金属离子、无机阴离子、有机络合剂对单纯铜类-Fenton反应降解有机物的影响,同时初步探讨了单纯铜类Fenton体系及复杂铜类Fenton体系的反应机理。结果表明:在常温条件下,单纯的Cu2+-H2O2体系中,当pH为5.5,Cu2+为0.8 mmol/L,H2O2为0.08 mol/L,180 min后硝基苯的去除率可达94.67%,有机物的降解率达到最大。铜催化的类芬顿反应所生成的活跃氧化物的性质对于pH有很强的依赖性,在酸性条件下,羟基自由基是主要的活性氧化物,而在微酸性和中性、碱性条件下,羟基自由基和高价态的铜氧化物是同时参与反应并且相互兼容的,并且体系的pH越高,高价态的铜氧化物的含量也越大。在铜类Fenton体系中,硝基苯在降解过程中会生成对苯二酚、4-硝基邻苯二酚、硝基对苯二酚、苯醌等中间产物,这些中间产物会促进Cu2+向Cu+的转化,增大了高氧化性能的活性物质的生成量,从而提高了类-Fenton反应降解硝基苯的速率。铜类-Fenton降解硝基苯的反应具有自催化作用。Ni2+会抑制Cu2+-H2O2体系中硝基苯的降解,然而Mn2+对于Cu2+-H2O2体系中硝基苯的降解却有明显的促进作用。无极阴离子ClO4-、Cl-、NO3-、H2PO42-对于Cu2+-H2O2体系氧化降解硝基苯都有显著的抑制作用。有机络合剂乙二胺四乙酸(EDTA)对于铜催化的类芬顿反应有显著的抑制作用,氨三乙酸(NTA)对于铜类-Fenton反应降解有机物是有相对较强的促进作用的,然而酒石酸(TA)对于Cu2+-H2O2体系中硝基苯的氧化降解却有明显的促进作用。
[Abstract]:Copper electroplating wastewater contains a lot of organic pollutants and metal copper ions. Copper ions as transition metal ions of 3D orbital have similar properties as iron ions, and can also catalyze the decomposition of hydrogen peroxide to produce active substances with high oxidation performance.In this study, the copper plating wastewater, which accounts for 20% of the electroplating wastewater, was used as the simulation object, and the copper ion in the electroplating wastewater was used as the catalyst. Hydrogen peroxide, which was green, efficient, cheap and easy to obtain, was added as the oxidant, which had little influence on the environment.The degradation of organic substrates by the active substances with high oxidation performance in the reaction process not only saves the cost, but also eliminates the interference of organic matter by the reuse treatment of metal ions.On the basis of pure copper Fenton system, the effects of transition metal ions, inorganic anions and organic complexing agents on the degradation of organic compounds by pure copper Fenton reaction were studied.The reaction mechanism of pure copper Fenton system and complex copper Fenton system was also discussed.The results show that the removal rate of nitrobenzene can reach 94.67 and the degradation rate of organic matter is the highest in the pure Cu2 H _ 2O _ 2 system at room temperature when pH = 5.5 渭 mol / L ~ (2 +) = 0.8 mmol / L ~ (2 +) H _ 2O _ (2) = 0.08 mol / L ~ (-1) ~ (180) min.The properties of active oxides produced by copper-catalyzed Fenton-like reactions are strongly dependent on pH. In acidic conditions, hydroxyl radicals are the main active oxides, while in slightly acidic, neutral and alkaline conditions, hydroxyl radicals are the main active oxides.Hydroxyl radical and high valence copper oxide are both involved in the reaction and compatible with each other, and the higher the pH of the system is, the higher the content of the high valence copper oxide is.In copper Fenton system, nitrobenzene can produce intermediate products such as hydroquinone 4-nitrocatechol, nitrohydroquinone, nitrohydroquinone and so on. These intermediates can promote the transformation of Cu2 to Cu.The production of active substances with high oxidation performance was increased, and the degradation rate of nitrobenzene was increased by Fenton-like reaction.The degradation of nitrobenzene in Cu2 H 2O 2 system was inhibited by Cu Fenton reaction. Ni2 could inhibit the degradation of nitrobenzene in Cu2 H 2O 2 system. However, Mn2 could promote the degradation of nitrobenzene in Cu2 H 2O 2 system.The non-polar anions ClO _ 4-O _ 3-O _ 3-O _ 2PO _ 4- can inhibit the oxidative degradation of nitrobenzene in the system of Cu2 H _ 2O _ 2.The organic complexing agent EDTA-EDTA-EDTA-EDTA has a significant inhibitory effect on the copper-catalyzed Fenton-like reaction, and NTAs has a relatively strong promoting effect on the degradation of organic compounds in the copper-Fenton reaction.However, tartaric acid (TAA) can promote the oxidative degradation of nitrobenzene in Cu2-H _ 2O _ 2 system.
【学位授予单位】：南昌航空大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：X781.1

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