【作者】 张凤梅；

【导师】 刘炳泗；

【作者基本信息】 天津大学 ， 化学， 2012， 博士

【摘要】 近年来，人们对金属氧化物作为高温煤气脱硫剂进行了深入的研究。为了解决金属氧化物的烧结、利用率低和粉化等技术难题，我们制备了高比表面积的介孔金属氧化物脱硫剂，并且研究了它们的高温煤气脱硫性能和稳定再生性能。采用湿法浸渍方法制备了不同Cu/Mn原子比例的Cu_xMn_y/SBA-15脱硫剂，并且在700-850℃的温度区间内测试了它们的脱硫性能。800℃条件下的Cu₁Mn₉/SBA-15的穿透（有效）硫容为13.8g单质硫/100g脱硫剂，其穿透硫容显著高于40wt%LaFeO₃/SBA-15和50wt%LaFe₂O_x/MCM-41在500-550℃条件下的穿透硫容（前者为4.8g-单质硫/100g-脱硫剂，后者为5.58g-单质硫/100g-脱硫剂）。这表明，湿法浸渍法制备的负载于SBA-15的Cu/Mn氧化物脱硫剂具有高热稳定性，其脱硫性能也大幅度提高。一定比例的氧化铜的掺杂保证了氧化锰具有较高的分散性，九次连续的800℃脱硫-再生循环性能测试显示，Cu₁Mn₉/SBA-15具有稳定的可再生性能。反应-再生前后样品的BET、HRTEM和SAXRD表征结果证实，使用前后脱硫剂的介孔结构依然紧致有序。为了提高脱硫剂在多次脱硫-再生循环的稳定性能，具有三维孔道结构的KIT-6被用于脱硫剂载体。我们采用湿法浸渍方法制备了不同La/Mn原子比例的La_xMn_y/KIT-6脱硫剂，并且在700-850℃温度区间内测试了它们的脱硫性能。800℃条件下La₃Mn₉₇/KIT-6脱硫性能最好，其穿透硫容为11.56g单质硫/100g脱硫剂。八次连续脱硫（800℃）-再生（600℃）循环测试结果表明，La₃Mn₉₇/KIT-6脱硫剂显示了良好的稳定再生性能，并且保持了80%的初始硫容。采用BET、XRD、HRTEM和H₂-TPR等多种手段对使用前后的脱硫剂进行了表征。新鲜样品和使用后样品的XRD谱图和HRTEM图像结果显示，采用KIT-6作为载体有效地抑制了Mn₂O₃的聚集，从而大幅度提高了其稳定再生性能。我们应用软模板法制备介孔无负载纯金属氧化物脱硫剂的探索性工作,考察了脱硫剂的脱硫活性，并且采用了BET及XRD等技术对其脱硫剂进行表征。更多还原

【Abstract】 In recent years, metal oxides as desulfurizer for hot coal gas desulfurization havebeen in depth studied. To solve these technical problems, such as sintering，lowutlization and pulverization, mesoporous metal oxides with large surface area wereprepared and the performance for hot coal gas desulfurization was investigated.A series of mesoporous Cu_xMn_y/SBA-15sorbents with different Cu/Mn atomicratios were prepared by wet impregnation method and their desulfurizationperformance in hot coal gas was investigated in the temperature range of700-850℃.The breakthrough sulfur capacity of Cu₁Mn₉/SBA-15observed at800°C is13.8gS/100g sorbents, which is remarkably higher than these of40wt%LaFeO3/SBA-15（4.8g S/100g sorbents） and50wt%LaFe₂O_x/MCM-41（5.58g S/100g sorbents） usedat500-550°C. This suggested that the loading of Mn₂O₃active species with highthermal stability to SBA-15support significantly increased sulfur capacity atrelatively higher sulfidation temperature. The successive ninedesulfurization-regeneration cycles at800°C revealed that Cu₁Mn₉/SBA-15presentedhigh performance with endurable regeneration ability due to the high dispersion ofMn₂O₃particles incorporated with a certain amount of copper oxides. The fresh andused Cu_xMn_y/SBA-15sorbents were characterized by means of BET, XRD, andHRTEM techniques, confirmed that the structure of the sorbents remained intactbefore and after hot coal gas desulfurization.To enhance the stability of sorbent during continuous desulfurization-regenerationcycles, KIT-6with3-D pore channels was applied as support for desulfurizers. Aseries of mesoporous La_xMn_y/KIT-6sorbents with different La/Mn atomic ratio werefabricated by wet impregnation method and their desulfurization properties for hotcoal gas desulfurization were investigated in the temperature range of700-850℃.La₃Mn₉₇/KIT-6performed the best at800℃with breakthrough sulfur capacity of11.56g sulfur/100g sorbent. The successive eight desulfurization （800℃）-regeneration （600℃） cycles revealed that La₃Mn₉₇/KIT-6performed well withendurable regeneration ability, which obtained80%of its initial sulfur capacity. Thefresh and used La_xMn_y/KIT-6sorbents were characterized by means of BET, XRD,HRTEM and H₂-TPR techniques. The XRD patterns and HRTEM images of fresh andused La₃Mn₉₇/KIT-6confirmed that the utilization of KIT-6suppressed the aggregation of Mn₂O₃particles effectively and improved the stability of sorbent.Some attempts were tried to fabricate mesoporous metal oxides by usingsoft-template method. The performance of sorbents was investigated and the sorbentwas characterized by means of BET and XRD techniques.更多还原