基于湿式催化氧化技术的含铜金属—有机骨架催化剂研究

发布时间：2018-01-23 18:40

  本文关键词： 酚类有机废水 Cu-MOFs GrO/HKUST-1复合组分 催化湿式过氧化氢氧化 羟基自由基　出处：《东南大学》2016年硕士论文　论文类型：学位论文

【摘要】：随着化工行业的发展,酚类有机废水的排放日益增多,导致严重的环境污染,使得酚类有机废水的处理备受关注。催化湿式过氧化氢氧化技术因较温和的操作条件和较好降解效果,成为酚类有机废水处理的研究热点。MOFs材料因具有较大的比表面积和规整可控的孔结构使其在催化领域表现出较好的应用前景。将Cu-MOFs作为非均相催化剂应用于湿式催化氧化苯酚废水,有着其它催化剂无法媲美的优势。本文采用溶剂热法制备了HKUST-1和Cu(BDC)两种不同的Cu-MOFs材料。HKUST-1和Cu(BDC)分别为八面体结构和六面体结构。且Cu在两种MOFs中的含量分别为24.18%,15.21%。分别将两种Cu-MOFs作为非均相催化剂,以H202为氧化剂,来催化降解苯酚废水。考察了反应温度、催化剂用量、H202用量、苯酚废水的pH等条件对Cu-MOFs催化降解苯酚的影响。此外还研究了Cu-MOFs的重复利用性能和稳定性,初步考查了其催化降解机理。结果表明：Cu(BDC)骨架表现出比HKUST-1骨架更好的催化活性,当温度为60℃,H2O2用量为1.0 mL, Cu(BDC)的用量为20 mg,苯酚溶液的初始pH为6.65时,Cu(BDC)催化降解苯酚达到最佳效果,此时,苯酚的转化率为99%,COD的去除率为93%。重复利用两次后,Cu(BDC)骨架仍然能保持较好的催化活性,苯酚的转化率能达到99%,COD的去除率能达到85%以上。类似于其它催化剂,Cu(BDC)湿式催化氧化苯酚也是遵循羟基自由基机理。并且Cu(BDC)表现出较好的稳定性,Cu2+的浸出量仅为7ppm。本文采用溶剂热法合成了GrO含量分别为1wt%,3 wt%和5wt%的GrO/HKUST-1复合组分,并分别将其作为非均相催化剂进行苯酚的催化降解。结果表明：加入GrO后没有阻止HKUST-1骨架的形成,大部分的HKUST-1晶体仍然保持八面体结构,且GrO附着在HKUST-1晶体的表面。随着GrO掺杂量的增加,所形成的GrO/HKUST-1复合组分催化剂对苯酚的催化降解活性先提高后降低。当GrO的含量为3wt%时,GrO-3/HKUST-1复合组分催化剂的活性最高。较高的温度有利于GrO-3/HKUST-1复合组分催化剂催化氧化苯酚。GrO-3/HKUST-1复合组分催化剂在pH=4-9内都表现出较好的催化活性,表明GrO-3/HKUST-1复合组分催化剂具有较强的抗酸碱性能。掺杂GrO后,GrO-3/HKUST-1复合组分催化剂具有较好的重复利用性能,且GrO-3/HKUST-1催化降解苯酚依然依赖于羟基自由基。
[Abstract]:With the development of chemical industry, the discharge of phenolic organic wastewater is increasing day by day, resulting in serious environmental pollution. The treatment of phenolic organic wastewater has attracted much attention. Catalytic wet hydrogen peroxide oxidation technology is more effective because of mild operation conditions and better degradation effect. Because of its large specific surface area and regular and controllable pore structure, MOFs have a good application prospect in the field of catalysis. Homogeneous catalyst is used in wet catalytic oxidation of phenol wastewater. In this paper, two different kinds of Cu-MOFs materials, HKUST-1 and CuBDC, were prepared by solvothermal method. HKUST-1 and Cu( 2) were prepared by solvothermal method. BDC is octahedron and hexahedron respectively, and the content of Cu in the two kinds of MOFs is 24.18%. 15.21. two kinds of Cu-MOFs were used as heterogeneous catalysts and H202 as oxidant to catalyze the degradation of phenol wastewater. The reaction temperature and the amount of catalyst were investigated. The effect of pH of phenol wastewater on the degradation of phenol catalyzed by Cu-MOFs was studied. The reusability and stability of Cu-MOFs were also studied. The catalytic degradation mechanism of the catalyst was investigated. The results showed that the HKUST-1 skeleton exhibited better catalytic activity than the HKUST-1 skeleton, and the amount of H _ 2O _ 2 was 1.0 mL at 60 鈩，

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