Co-Cr-O复合氧化物上丙烷低温完全氧化:结构效应、反应动力学和原位光谱研究

doi:10.1016/S1872-2067(19)63480-7

摘要/Abstract

摘要： 低碳烷烃是一类主要的挥发性有机污染物（VOCs），广泛生成于汽车尾气以及各种工业过程如煤处理、石油精炼以及天然气处理等.随着对环保要求的日益提高，对高效VOCs消除技术的需求愈加迫切.催化完全氧化（催化燃烧）技术具有起燃温度低、能耗低、净化效果好（无二次污染）等优点，因而极具应用潜力.对于低碳烷烃的催化燃烧，贵金属催化剂如Pt和Pd等具有很高的反应活性，但存在价格昂贵并易中毒等缺陷限制了其商业应用.另一方面，过渡金属氧化物由于其价格低廉、抗中毒性能优异及热稳定性好等特点受到广泛关注.Cu，Mn，Co，Fe等氧化物都具有良好的催化活性，其中Co氧化物由于其在丙烷催化燃烧中的高活性受到关注.而在Co氧化物中添加第二金属更能促进其反应性能.因此本文制备了一系列不同Co/Cr比例的复合氧化物用于丙烷催化燃烧，考察了催化剂结构和表面性质对其反应行为的影响，并通过反应动力学和原位光谱技术对反应机理进行了探索.
实验结果表明，随着Co/Cr比例的变化，催化剂的晶相结构、颗粒尺寸、比表面积、表面酸性以及氧化还原性等特性均发生了明显变化，进而影响了其反应行为.当Co/Cr比例为1/2时（1Co2Cr），催化剂为尖晶石结构并具有最大的比表面积.该催化剂上具有最高的反应活性（250℃时反应速率为1.38μmol g^-1 s^-1），可归因于其最高的表面酸性和低温氧化还原性能的协同作用.反应动力学结果表明，1Co2Cr催化剂上丙烷和氧气的反应级数分别为0.58 ±0.03和0.34 ±0.05，低于2Co1Cr（分别为0.77 ±0.02和0.98 ±0.16）和1Co5Cr（分别为0.66 ±0.05和1.30 ±0.11），表明1122Cr催化剂相比后二者具有更高的丙烷和氧气表面覆盖度，得益于其更高的表面酸性和更好的低温氧化还原性能.此外，原位红外光谱表明，在反应过程中，1Co2Cr催化剂上的主要表面物种为多齿碳酸盐，该物种在低温时（< 250℃）在表面积聚，但在高温时被分解.

关键词: 丙烷催化燃烧, Co-Cr复合氧化物, 氧化还原性能, 表面酸性, 反应动力学

Abstract: A series of Co-Cr-O mixed oxides with different Co/Cr molar ratios are synthesized and tested for the total oxidation of propane. The reaction behaviors are closely related to the structural features of the mixed oxides. The catalyst with a Co/Cr molar ratio of 1:2 (1Co2Cr) and a spinel structure has the best activity (with a reaction rate of 1.38 μmol g^-1 s^-1 at 250℃), which is attributed to the synergistic roles of its high surface acidity and good low-temperature reducibility, as evidenced by the temperature-programmed desorption of ammonia, reduction of hydrogen, and surface reaction of propane. Kinetic study shows that the reaction orders of propane and oxygen on the 1Co2Cr catalyst (0.58 ± 0.03 and 0.34 ±0.05, respectively) are lower than those on the 2Co1Cr catalyst (0.77 ±0.02 and 0.98 ±0.16, respectively) and 1Co5Cr (0.66 ±0.05 and 1.30 ±0.11, respectively), indicating that the coverages of propane and oxygen on 1Co2Cr are higher than those on the other catalysts due to its higher surface acidity and higher reducibility. In addition, in-situ diffuse reflectance infrared spectroscopic investigation reveals that the main surface species on 1Co2Cr during the reaction are polydentate carbonate species, which accumulate on the surface at low temperatures (< 250℃) but decompose at relatively high temperatures.

Key words: Propane combustion, Co-Cr mixed oxides, Reducibility, Surface acidity, Kinetics

中图分类号:

廖文敏, 赵培培, 岑丙横, 贾爱平, 鲁继青, 罗孟飞. Co-Cr-O复合氧化物上丙烷低温完全氧化:结构效应、反应动力学和原位光谱研究[J]. 催化学报, 2020, 41(3): 442-453.

Wen-Min Liao, Pei-Pei Zhao, Bing-Heng Cen, Ai-Ping Jia, Ji-Qing Lu, Meng-Fei Luo. Co-Cr-O mixed oxides for low-temperature total oxidation of propane: Structural effects, kinetics, and spectroscopic investigation[J]. Chinese Journal of Catalysis, 2020, 41(3): 442-453.

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