Yang Yonglai, Xu Hengyong, Li Wenzhao
Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, People's Republic of China.
J Nanosci Nanotechnol. 2004 Sep;4(7):891-5. doi: 10.1166/jnn.2004.118.
Characteristics of carbon deposition by CH4 and carbon elimination by CO2 over conventional and nanoscale Ni/gamma-Al2O3 catalysts were investigated by using a pulse reaction, as well as by TGA, TEM, TPO-MS, H2-TPR and H2-chemisorption techniques. It was found that the behaviors of carbon deposition by CH4 decomposition and carbon elimination by CO2 depend on the active metal dispersion and the metal-support interaction. The filamentous carbon was formed on the conventional Ni/gamma-Al2O3 catalyst with low metal dispersion and relatively large particles, this type of filamentous carbon was far from the active centers and difficult to eliminate by CO2. On the other hand, the carbon deposition originated from CH4 decomposition on the nanoscale Ni/gamma-Al2O3 catalyst would mainly cover the surface of active centers, this type of highly active carbon was easily eliminated by CO2 because it is close to the active center Ni atoms. As a result, the improvement of coking-resistance was ascribed to the high metal dispersion and strong metal-support interaction, a model of CH4 decomposition carbon deposition on Ni/gamma-Al2O3 catalyst was proposed.
采用脉冲反应以及热重分析(TGA)、透射电子显微镜(TEM)、程序升温氧化-质谱联用(TPO-MS)、氢气程序升温还原(H2-TPR)和氢气化学吸附等技术,研究了常规和纳米级Ni/γ-Al2O3催化剂上CH4的积碳特性和CO2的消碳特性。结果发现,CH4分解积碳和CO2消碳行为取决于活性金属的分散度以及金属-载体相互作用。在金属分散度低且颗粒相对较大的常规Ni/γ-Al2O3催化剂上形成丝状碳,这种丝状碳远离活性中心,难以被CO2消除。另一方面,纳米级Ni/γ-Al2O3催化剂上由CH4分解产生的积碳主要覆盖活性中心表面,这种高活性碳因靠近活性中心Ni原子而容易被CO2消除。因此,抗结焦性能的提高归因于高金属分散度和强金属-载体相互作用,并提出了Ni/γ-Al2O3催化剂上CH4分解积碳的模型。