A series of cobalt-based catalysts with different supports have been prepared using impregnation method, and characterized by X-ray diffraction (XRD), laser Raman (LR), and infrared spectroscopy (IR). The catalytic activities for methane combustion were assessed in a micro-reactor. The ZrO2 and Al2O3 supports are themselves active in methane combustion, and ZrO2 supported cobalt catalyst was found to have the highest activity amongst the TiO2, Al2O3, MgO supported catalysts and bulk Co3O4. The Co content has a marked effect on the activity of the ZrO2 supported catalyst with 1.0 and 15 wt.% of Co having the lowest light-off temperature in methane combustion. In the MgO supported catalyst, Co oxide was highly dispersed over the MgOsupport surface or enters the lattice ofMgOto form a solid solution, whose activity for methane combustion is reasonable. The zirconia supported cobalt catalysts are very active and stable when calcination or reaction temperature is no more than 900◦C. Calcining the catalysts at temperatures above 900℃ for more than 1h decreases the catalyst activity. The deactivation of the catalyst probably results from the decrease of the surface area.

Investigation on molybdenum carbide catalyst, its oxide precursor and its modifiers was performed using temperature programmed surface reaction (TPSR) technique, BET surface specific area and X-ray diffraction (XRD) measurement. The carbide catalyst and its modifiers were evaluated using microreactor apparatus. The evaluation result showed that the addition of nickel promoted the POM to syngas, the addition of copper exhibited weaker promotion at the initial stage, but it turned unfavorable to the POM to syngas hereafter. As for potassium doped catalyst, it was unfavorable to the POM. According to the characterizations, the effect of added metals on the carburization, especially under the condition of POM, was elucidated.

考察了反应温度、气体空速和进料中CH4∶O2比值对Mo2C/Al2O3催化的POM反应制合成气的影响。结果发现较高的温度具有较高的甲烷转化率、CO和H2的选择性；而在较低的温度下，对CO的选择性比对H2的影响更大。反应气体的空速较小时对于甲烷的转化率、CO和H2的选择性是有利的；而在较高的气体空速下，氢气的选择性则更低。进料中CH4∶O2 比值稍高于2∶1时有利于获得高的甲烷转化率、CO和H2的选择性，并且还可以增加催化剂的稳定性。当CH4∶O 2比值低于2∶1时，甲烷转化率、CO和H2选择性随反应的进行急剧下降，而当此比值调整到高于2∶1时，转化率和选择性都可以得到恢复。

制备了不同组分Na、W、Mn/SiO2催化剂，在ITD（Ion Trap Detector）装置上进行了催化剂表面CO恒温脉冲反应（CO-CTPR）。 研究结果表明，单组分Na、W、Mn/SiO2催化剂体相晶格氧向表面扩散的速度顺序为Mn/SiO2/Na/S iO2/W/SiO2；与CO反应的表面晶格氧数量的顺序为M n/SiO2/Na/SiO2≈W/SiO2。多组分Na、W、Mn/SiO2催化剂体相晶格氧向表面扩散的速度顺序为Na-W/SiO2/Na-Mn/SiO2/W-Mn/SiO2/Na-W-Mn/SiO2，且Na与W、Mn的结合对体相晶格氧向表面的扩散有促进作用；与CO反应的表面晶格氧数量的顺序为Na-W-Mn/SiO2/Na-Mn/SiO2/W-Mn/SiO2/Na-W/S iO2。

制备了一系列不同Mo2C担载量的Mo2C/Al2O3催化剂，利用微型固定床反应器对其POM反应进行了活性评价,并采用XRD、SEM和BET等方法进行了结构表征。实验结果表明，纯Mo2c催化剂在反应初期有较高的CH4转化率，但CO和H2的选择性很低，随着反应时间的增加，CH4转化率急剧下降，Mo2C担载量小于24.8%的摧化剂，随担载量增加，CH4转化率明显升高。同时，随着反应时间的增加，CH4转化率有所下降，CO和H2的选择性则明显升高。Mo2C担二项式国量在35.4～42.5%的摧剂，具有好的CH4转化率和CO、H2选择性，但担载量过高时，CH4转化率会随反应时间的增加而下降。结构表征表明，未担载的和担载的碳化物催化剂均为β-Mo2C，担载量小于10.6%，Mo2C高度分散于Al2O3表面，担载量较高时，Mo2c颗粒变大，比表面减少。