催化湿式氧化法（CWPO）处理染料废水的实验研究

【作者】 卢堂俊；

【导师】 李剑超；

【作者基本信息】 陕西师范大学 ， 环境科学， 2010， 硕士

【摘要】 印染废水因为色度大,毒性大,废水大多呈碱性,水质比较复杂等特点,对环境和人类的生命健康造成很大的危害,所以对印染废水的无害化处理已经成为印染工业和环境保护的一项重要难题。目前,对印染废水的处理方法主要有生物方法、化学方法、物理-化学方法和基于其它高端技术的其它方法,在处理中大多相互协作。其中化学方法中的催化湿式氧化法因为其效率高、反应快、二次污染小、处理条件温和等优点,已经成为一种对印染废水处理很有发展前景的技术,逐渐得到研究者的关注。印染废水中残存的染料分子是造成印染废水色度大和COD高的主要原因,因此对染料分子的去除具有很实际的意义。本文选择10种染料分别配制模拟染料废水,以沸石为载体,负载10种活性金属制备催化剂,并研究各催化剂在催化湿式氧化法中对所配制的染料废水的降解率,评价各活性金属的催化活性；然后,选择Cu, La和Mo三种金属做为催化剂活性组分,配制混合浸渍液,制备Z/CLM材料,并采用催化湿式氧化法对直接紫D-BL,直接灰BN和酸性黑10B三种染料进行降解。研究催化剂制备中金属活性组分的比例、焙烧条件、沸石载体粒径、活性组分浸渍量和其它制备条件对催化效果的影响,并对Z/CLM材料进行结构表征。使用最佳制备条件的Z/CLM材料做为催化剂,考察研究催化湿式氧化法处理直接紫D-BL的处理条件,如H202的添加量的影响、溶液中的盐浓度的影响、溶液的pH值影响、处理温度和处理时间的影响,并对材料做流化床模拟实验和再生实验,最后对整个反应机理做简单的讨论。实验结果表明：(1)使用金属Cu、La、Mo、Zr、Fe负载制备的催化剂在催化湿式氧化中有较好的催化活性；制备催化剂Z/CLM材料的最佳制备条件为浓度使用Cu:La:Mo= 0.5:0.5:0.2 (mol·L-1)的混合金属盐溶液,与60-80目的天然沸石以固液比1：1(ml：g)浸渍,并在600℃条件下焙烧0.5 h；(2)所制备的Z/CLM材料在催化湿式氧化法中对模拟染料废水有很好的去除效果,当Z/CLM材料使用量为0.20 g,直接紫D-BL染料废水中H202为8.33 ml·L-1, NaCl浓度为5.84g·L-1, pH为7.10,处理温度为35℃,处理时间5 h时,对模拟染料废水直接混纺紫D-BL的去除率可达95.15%；而且,废水的温度和所含NaCl浓度对去除效果有促进作用,pH在酸性和弱碱性条件下均有较高的去除率；(3)对Z/CLM材料进行动态流化床研究得,Z/CLM材料对直接混纺紫D-BL的去除能力为37.82 mg·g-1；材料再生实验表明,材料的再生性差；(4)对催化湿式氧化法反应机理的分析表明,整个反应过程是一个HO·的反应。更多还原

【Abstract】 Printing and dyeing wastewater was very complex and characterized by heavy colority, high toxicity, alkaline and. It caused great harm to the environment and human health, so innocuous treatment of dyeing wastewater has become an important problem in printing and dyeing industry and the environment protection. Currently, bleaching methods mainly include biology method, chemical methods, physical-chemical and other ways generated by high-end technologies, the most common method was the mutual cooperation in the treatment of dyeing wastewater. CWPO (Catalytic Wet Peroxide Oxidation) has bocome a promising technology because of its high efficiency, response speed, small secondary pollution, and moderate treatment conditions, etc. Therefore, researchers gradually pay great attention on it.The residual dye molecules of printing and dyeing wastewater are the main reason to cause the heavy colority and high COD, so it has a very practical significance to remove the dye molecules. In this paper, ten kinds of azo dyes were prepared to simulate printing and dyeing wastewater. And catalysts were prepared by loading ten active metals with zeolite used as carrier. The dye removal rates of diverse catalysts were studyed in CWPO, the metal catalytic activity were also evaluated. Then, three metals (Cu, La and Mo) were selected as the active catalysts, mixed soaking liquid were prepared, a novel kind of metal loaded material, zeolite catalyst (Z/CLM), were prepared. Besides, degradation of three kinds of dyes(direct purple D-BL, direct grey BN, acid black 10B) were also researched. Lots of factors were characteristed, such as the ratio of the active metal, roasting conditions, zeolite particle size, dipping amount of active component, other preparation conditions on the catalytic effect and the structure of Z/CLM materials. Using the optimum Z/CLM material prepared on best conditions as a catalyst to investigate the treatment conditions of direct purple D-BL in CWPO. For instance, the addition amount of H2O2, the concentration of the solution, solution pH, treating temperature and processing time. And the tests of the simulation fluidized bed and regeneration were also carried, finally a simple discussion had been done on the reaction mechanism.The results showed that:(1) The zeolite catalysts loaded Cu, La, Mo, Zr and Fe had better catalytic activity in CWPO. And the optimum conditions of the material preparation were natural zeolite 60-80 mesh count, gradually dipping with salt-mixture solution Cu:La:Mo=0.5:0.5:0.2 (mol·L-1) by solid-to-liquid ratio 1:1, calcinated at 600℃for 0.5h. (2) Z/CLM materials had better removal efficiency in CWPO, the decolorization rate of direct purple D-BL can reach 95.15% under the optimum condition, H2O2 8.33 ml·L-1, the concentration of NaCl 5.84 g·L-1, pH 7.10, temperature 35℃, the processing time 5h. Moreover, the temperature of wastewater and the concentration of NaCl had promotion to the removal efficiency, and the material had a higher removal rate in acidic and weak base pH conditions.(3) Besides, dynamic fluidized bed experiment indicated the removal ability to direct blending purple D-BL was 37.82 mg·g-1, and recycling experiments showed that the regeneration of the material was poor.(4) Reaction mechanism of catalytic wet peroxide oxidation evinced that the reaction was a reaction of HO·.更多还原