氧化铝负载纳米铜基脱硫剂的制备及脱硫效能研究

发布时间：2018-01-09 11:36

本文关键词：氧化铝负载纳米铜基脱硫剂的制备及脱硫效能研究　出处：《哈尔滨理工大学》2015年硕士论文　论文类型：学位论文

【摘要】：为了提高纳米脱硫剂活性组分利用率，提高脱硫活性，降低其使用成本，解决脱硫剂再生难等问题，本研究拟开发一种脱硫效果好，性能稳定，可再生的负载型纳米铜基脱硫剂，为工业化应用提供技术参数。论文采用等体积浸渍法和共沉淀法制备出氧化铝负载型纳米铜基脱硫剂，以H2S为目标污染物，通过固定床反应器对制备出的脱硫剂进行脱硫活性评价，探讨制备条件对脱硫活性的影响因素，确定最佳的制备工艺；利用多种测试技术对所制得负载型纳米脱硫剂进行表征，分析脱硫剂的结构对脱硫效能的影响，并考察了助剂(Ce，Fe，Co，Zn)对CuO/Al2O3脱硫活性和稳定性的影响；探讨再生温度和再生气氛等工艺对CuO/Al2O3再生性能的影响，并进行多周期的硫化/再生循环实验。结果表明共沉淀法制备脱硫剂脱硫效果明显好于浸渍法，当共沉淀剂为NaOH，焙烧温度为400℃，，焙烧时间3h，活性组分最佳的负载比例70%时，H2S穿透时间为490min，硫容为140mg g-1，铈掺杂到CuO/Al2O3中能使脱硫活性和稳定性进一步提高；结构分析显示，共沉淀法制备的CuO/Al2O3中纳米氧化铜的晶粒尺寸远小于浸渍法，且Al2O3抑制了氧化铜晶粒的生长。采用XPS表征技术分析了CuO/Al2O3脱硫剂的硫化产物，结合硫化产物的TG曲线和XRD衍射图，分析结果表明，存在着CuS和CuSO4两种脱硫产物。采用热再生法在氧化或还原氛围下对共沉淀法制备掺杂助剂的Ce-CuO/Al2O3，Fe-CuO/Al2O3，Co-CuO/Al2O3，Zn-CuO/Al2O3样品的再生性能进行研究。研究表明，再生效果较好的脱硫剂是Ce-CuO/Al2O3和Zn-CuO/Al2O3。Ce-CuO/Al2O3纳米脱硫剂在NH3气氛下的再生效果要优于氧气氛，650℃时脱硫剂可进行四次再生，累积脱硫剂穿透时间达803min，累积硫容达229.4mg·g-1；但Zn-CuO/Al2O3脱硫剂正相反，氧气氛下的再生效果更好，600℃时四次再生后的累积H2S穿透时间达755min，累积硫容达215.7mg g-1。
[Abstract]:In order to improve the utilization rate of desulfurizer activated nano group, improve the desulfurization activity, reduce its cost, solve the problem of desulfurizer regeneration difficult, this study intends to develop a good desulfurization effect, stable performance, supported nano copper based sorbents renewable, provide technical parameters for the industrial application.
The paper by impregnation method and were prepared by nano copper based sorbents supported on alumina, taking H2S as a target pollutant, the desulfurization activity evaluation of desulfurization agent for the preparation by fixed bed reactor, to explore the influence factors of preparation conditions on the desulfurization activity, determine the best preparation process of; prepared were characterized using a variety of desulfurization agent supported nano testing technology, structure analysis of desulfurization agent on desulfurization efficiency, and the effects of additives (Ce, Fe, Co, Zn) of CuO/Al2O3 desulfurization activity and stability; to explore the effects of regeneration temperature and regeneration atmosphere regeneration process on the performance of CuO/Al2O3, sulfide / and multi cycle recycling experiments.
The results show that the coprecipitation desulfurization effect is obviously better than the impregnation method, the co precipitation agent NaOH, calcination temperature of 400 DEG 3h, roasting time, active component load ratio of 70% when the optimal H2S penetration time is 490min, the sulfur content of 140mg g-1, CE doped into CuO/Al2O3 can make the desulfurization activity and further improve the stability;
The structure analysis shows that the grain size of nano copper oxide prepared by CuO/Al2O3 is much smaller than the impregnation coprecipitation, and the inhibition of Al2O3 copper oxide grain growth. Analysis of sulfurized CuO/Al2O3 desulfurizer characterized by XPS technology, combined with the curing product TG curve and XRD diffraction analysis results show that the existence of CuS and CuSO4 two kinds of desulfurization products.
The thermal regeneration method in oxidizing or reducing atmosphere on the preparation of doped additives by coprecipitation method Ce-CuO/Al2O3, Fe-CuO/Al2O3, Co-CuO/Al2O3, Zn-CuO/Al2O3 of regeneration performance of samples. The results show that better regeneration desulfurization agent is Ce-CuO/Al2O3 and Zn-CuO/Al2O3.Ce-CuO/ regeneration effect of Al2O3 nano desulfurizing agent in NH3 atmosphere is better than that of oxygen atmosphere at 650 DEG. The desulfurization agent can be four times the cumulative desulfurizer regeneration, the breakthrough time was 803min, the cumulative sulfur capacity 229.4mg g-1; but Zn-CuO/Al2O3 desulfurizing agent on the contrary, better regeneration effect in oxygen atmosphere at 600 DEG C, the cumulative H2S after four times regeneration penetration time was 755min, the cumulative sulfur capacity of 215.7mg g-1.

【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】：X701.3

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