【作者】 莫流业；

【导师】 郑小明；

【作者基本信息】 浙江大学 ， 有机化学， 2002， 博士

【摘要】 甲烷部分氧化制合成气是目前比较具有应用前景的甲烷利用途径之一。但该反应在催化剂床层中存在热点并且CH₄和氧气的混合物容易爆炸，因此甲烷部分氧化难以得到工业应用。甲烷二氧化碳重整制合成气近年来引起全世界学术界和产业界的广泛关注，但该反应是强吸热反应，能耗大并且催化剂易于积炭，因此该工艺过程亦难得到工业应用。近年来，甲烷部分氧化与甲烷二氧化碳重整耦合反应制合成气引起了广大研究者的兴趣。甲烷部分氧化与甲烷二氧化碳重整耦合制合成气具有以下优点：（1）能量耦合（甲烷部分氧化的放热与甲烷二氧化碳重整的吸热耦合）；（2）产物H₂／CO可根据后续工艺的需要进行调节；（3）O₂的加入在一定程度上可以减少催化剂的积炭。（4）两反应的耦合减少了空气的用量，亦即减少了合成气中N₂的含量，这样在多数场合下不需昂贵的空分设备，大大节约了生产成本。该工艺过程不仅具有甲烷部分氧化和甲烷二氧化碳重整的优点而且克服了甲烷部分氧化和甲烷二氧化碳重整反应的缺点。因此该工艺过程可望在近年内得到工业应用。本文以固定床为反应器对钴基催化剂进行研究；以流化床为反应器对镍基催化剂进行研究，均取得了比较有意义的结果。 第二章以固定床为反应器，使用XRD、TPR技术研究了载体以及活性组分钴的负载量对钴催化剂的影响，首次发现以Co／α—Al₂O₃催化剂是甲烷部分氧化与甲烷二氧化碳重整耦合反应的高活性催化剂。结果表明，金属与载体之间相互作用的强弱是影响催化剂性能的重要因素。以SiO₂为载体的Co／SiO₂由于金属—载体作用太弱对甲烷部分氧化与甲烷二氧化碳重整制合成气没有重整活性，只发生甲烷的燃烧反应；以γ—Al₂O₃更多还原

【Abstract】 The reaction of partial oxidation of methane to syngas has been one of the most promising CH₄ utilization approaches. But it will lead to hot-spot in catalyst bed for it is exothermic reaction and the mixture of CH₄ and O₂ is explosive gas, which are danger for large industrial scale. In recent years, the reaction of CO₂ reforming of CH₄ to syngas has been focused on by industrial and academic workers all over the world. But it is difficult to be applied in industry because this reaction is highly energy consumption and the catalyst for this reaction is prone to carbon deposition. Recently, the combined partial oxidation and CO₂ reforming of CH₄ has been attracted attention by researchers all over the world for it have many advantages compared to partial oxidation of CH₄ and CO₂ reforming of CH₄. Firstly, by coupling the exothermic partial oxidation reaction with the endothermic reforming reaction, the methane-to-syngas conversion can be operated in a safer manner than the reforming process. Secondly, by changing the feed composition, one can control the product ratio of H₂/CO according to the need of the postprocess. Thirdly, the combined reaction can decrease the carbon deposition greatly than the CO₂ reforming of CH₄ reaction. Finally, the combined reaction can reduce the consumption of air, that is it can reduce the content of N₂ in syngas, and in many cases the air separated equipment is not needed, so it can economize the investment of operation. In a word, the combined reaction has the advantage of both partial oxidation of methane and CO₂ reforming of CH₄, and it更多还原