纳米铜基复合脱硫材料的制备及硫化再生性能研究

发布时间：2018-04-18 06:31

本文选题：氧化铜 + 脱臭　；参考：《哈尔滨理工大学》2015年硕士论文

【摘要】：针对恶臭污染源排放恶臭气体的特点，有必要开发廉价且能够在室温下脱除恶臭气体的材料。而室温条件下为了提高脱硫剂的活性，就要减小脱硫剂的粒径，降低开发成本，因此研究高活性的室温纳米铜基脱硫剂具有重要的意义。采用直接沉淀法制备出元素掺杂改性的纳米铜基复合材料，探讨了脱硫剂结构与脱硫性能的关系。研究表明，单元素掺杂均可使纳米氧化铜脱硫剂的脱硫活性提高，其中铁、钴和铈元素的掺杂对纳米氧化铜活性的提高要略好于锌掺杂；双元素掺杂中Fe/Zn/CuO和Co/Ce/CuO复合脱硫剂的活性最具优势，当Fe:Zn:Cu原子比为2:1:25时（Fe/Zn/CuO），其H2S的穿透时间为400min；Co:Ce:Cu原子比为3:3:50时（Co/Ce/CuO），其H2S的穿透时间可达到540min，且两种脱硫剂对甲硫醇也具有较好的脱除效果。XRD、TEM和XPS等表征手段对元素掺杂纳米氧化铜的结构进行分析结果表明：不同元素掺杂到纳米氧化铜中，材料的主体成分仍为纳米氧化铜；XPS拟合数据显示，纳米氧化铜和元素掺杂后材料表面均含有Cu2+δ和Cu2+，且Cu2+δ/Cu2+的摩尔比值与脱硫剂活性呈现出明显的相关性，即Cu2+δ/Cu2+比值越大，脱硫效果越好。而Cu2+δ/Cu2+摩尔比值的增加，说明材料表面能形成更多的氧空位，有利于H2S中的硫和铜的结合，提高了脱硫活性。为研究纳米铜基复合材料的成型及硫化再生性能，通过对成型粘结剂的选择，确定了Fe/Zn/CuO的成型条件，并对其进行了再生实验研究。结果表明，成型后脱硫剂的有效成分为仍为氧化铜，成型后脱硫剂的机械强度增大，比表面积和孔体积减小，H2S的穿透时间能达到240min；同时，成型脱硫剂对硫化氢和甲硫醇均可进行再生使用，其中硫化氢可进行4次再生，累计穿透时间可达500min，，具备吸附多种硫系恶臭气体的能力，具有工业应用潜力。
[Abstract]:It is necessary to develop cheap materials which can remove odor gases at room temperature according to the characteristics of odor pollution sources.In order to improve the activity of desulfurizer at room temperature, it is necessary to reduce the particle size of desulfurizer and reduce the development cost. Therefore, it is of great significance to study the high-activity nano-cupric based desulfurizer at room temperature.Nano-copper matrix composites modified by elemental doping were prepared by direct precipitation method. The relationship between the structure of desulphurizer and desulfurization performance was discussed.The results show that the desulfurization activity of nano-copper oxide desulfurizer can be improved by single element doping, and the doping of iron, cobalt and cerium can improve the activity of nano-copper oxide slightly better than that of zinc doping.The activity of Fe/Zn/CuO and Co/Ce/CuO composite desulphurizer is the most advantageous in the double element doping.When the Fe:Zn:Cu atom ratio is 2:1:25, the penetration time of H _ 2S is 400min Co: ce: Cu = 3:3:50, and the penetration time of H _ 2S can reach 540mins. Moreover, the two desulfurizers have better removal effect for methylmercaptan. XRDX TEM and XPS have also been used to characterize the elemental doping of nanocrystalline.The results of structure analysis of copper oxide show that different elements are doped into nanometer copper oxide.Cu2 未 and Cu2 were found on the surface of nano-copper oxide and elemental doped materials, and the molar ratio of Cu2 未 / Cu _ 2 was significantly correlated with the activity of desulfurizer, that is, the larger the Cu2 未 / Cu _ 2 ratio, the higher the Cu2 未 / Cu _ 2 ratio.The better the desulphurization effect.The increase of the molar ratio of Cu2 未 / Cu 2 indicates that more oxygen vacancies can be formed on the surface of the material, which is favorable to the combination of sulfur and copper in H 2S and improves the desulfurization activity.In order to study the molding and vulcanization properties of nano-copper matrix composites, the forming conditions of Fe/Zn/CuO were determined through the selection of forming binder, and the regeneration experiments were carried out.The results showed that the effective component of the desulfurizer was still copper oxide, the mechanical strength of the desulfurizer increased, the penetration time of specific surface area and pore volume decreased to 240 min,Both hydrogen sulfide and methyl mercaptan can be regenerated by the molded desulfurizer. Hydrogen sulfide can be regenerated for 4 times, and the cumulative penetration time can reach 500 min. It has the ability to adsorb many kinds of sulfur malodorous gases and has the potential of industrial application.
【学位授予单位】：哈尔滨理工大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TB33;TQ131.21

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