MgO-Fe2O3/酸改性沸石催化降解磺胺甲噁唑的机理及生物毒性

Mechanism and biological toxicity of catalytic degradation of sulfamethoxazole using MgO-Fe2O3/acid-modified zeolite

  • 摘要: 为了避免催化剂流失及提高难降解有机废水处理效率,采用浸渍法制备MgO-Fe2O3/酸改性沸石催化剂(MFZ),通过X射线衍射、X射线光电子能谱、傅里叶红外光谱、扫描电镜-能谱等方法分析催化剂的结构和组成,研究臭氧浓度、初始溶液pH和催化剂投加量对磺胺甲噁唑(SMX)去除率和反应速率的影响,建立反应动力学模型,探索MFZ催化臭氧氧化SMX废水的降解途径和反应机制,并对MFZ催化剂浸出液进行植物毒性研究。结果表明:MFZ保留了天然沸石的高介孔骨架结构,比表面积、孔容和孔径分别为12.670 m2/g、0.044 cm3/g和4.012 nm,MgO-Fe2O3均匀负载于沸石表面,丰富的氧空位和表面羟基可促进O3分解产生·OH。MFZ催化臭氧氧化降解SMX遵循二级反应动力学模型,溶液初始pH对SMX去除率和反应速率的影响最大,SMX去除率最高可达83%,反应速率最高可达0.131 min−1。O3+MFZ体系降解SMX的过程由O3直接氧化和·OH间接氧化两部分组成,·OH起主要作用。SMX的分解主要通过氨基氧化和羟基化作用,以及杂环上的硫氮键和氮氧键的断裂来实现,矿化为二氧化碳、水等小分子物质;MFZ浸出液培养的小白菜平均根长和发芽指数比水培养的分别增加了10.3%和17.0%,可促进小白菜的发芽生长。

     

    Abstract: In order to avoid catalyst loss and enhance the treatment efficiency of refractory organic wastewater, MgO-Fe2O3/acid-modified zeolite catalyst (MFZ) was prepared by the impregnation method. The structure and composition of the catalyst were analyzed by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS), respectively. The effects of ozone concentration, initial solution pH, and catalyst dosage on the removal efficiency and reaction rate of sulfamethoxazole (SMX) were studied, and a reaction kinetics model was established. The degradation pathways and reaction mechanisms of SMX wastewater were explored using catalytic ozonation of MFZ, and the phyto-toxicity of MFZ catalyst leachate was evaluated. The results showed that MFZ retained the highly mesoporous framework structure of natural zeolite, and the specific surface area, pore volume, and pore size were 12.670 m2/g, 0.044 cm3/g, and 4.012 nm, respectively. MgO-Fe2O3 was uniformly loaded on the zeolite surface, and the abundant oxygen vacancies and surface hydroxyl groups could promote the decomposition of O3 to produce ·OH. The degradation of SMX using catalytic ozonation of MFZ followed a second-order reaction kinetics model. The initial pH of the solution had the greatest impact on the removal efficiency and reaction rate of SMX. The highest SMX removal efficiency of 83% and a corresponding reaction rate of 0.131 min−1 were achieved. The degradation process of SMX in the O3+MFZ system consisted of direct oxidation by O3 and indirect oxidation by ·OH, and ·OH played a major role. The decomposition of SMX was mainly achieved through amino oxidation and hydroxylation, as well as the breaking of sulfur-nitrogen bonds and nitrogen-oxygen bonds on the heterocyclic ring, resulting in mineralization into small molecules such as carbon dioxide and water. The average root length and germination index of Chinese cabbage cultured in the leachate of MFZ increased by 10.3% and 17.0%, respectively, compared to those in the water, which could promote the germination and growth of Chinese cabbage.

     

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