Chemical Engineering Department, Colorado School of Mines, Golden, Colorado 80401, USA.
J Phys Chem A. 2010 Jun 17;114(23):6502-14. doi: 10.1021/jp102049c.
A fundamental issue in the gasification of biomass is that in addition to the desired synthesis gas product (a mixture of H(2) and CO), the gasifier effluent contains other undesirable products that need to be removed before any further downstream processing can occur. This work assesses the potential to selectively remove hydrocarbons from a synthesis gas stream via gas-phase partial oxidation. Specifically, the partial oxidation of methane-doped, ethylene-doped, and methane/ethylene-doped model synthesis gas mixtures has been investigated at ambient pressures over a temperature range of 760-910 degrees C and at residence times ranging from 0.4 to 2.4 s using a tubular flow reactor. For the synthesis gas mixtures that contain either methane or ethylene, the addition of oxygen substantially reduces the hydrocarbon concentration while only a small reduction in the hydrogen concentration is observed. For the synthesis gas mixtures doped with both methane and ethylene, the addition of oxygen preferentially removes ethylene while the concentrations of methane and hydrogen remain relatively unaffected. These results are compared to the predictions of a plug flow model using a reaction mechanism that is designed to describe the pyrolysis and partial oxidation of small hydrocarbon species. The agreement between the experimental observations and the model predictions is quite good, allowing us to explore the underlying chemistry that leads to the hydrocarbon selective oxidation. The implications of these results are briefly discussed in terms of using synthesis gas to produce liquid fuels and electrical power via a solid oxide fuel cell.
生物质气化的一个基本问题是,除了所需的合成气产物(H(2)和 CO 的混合物)外,气化炉出口还含有其他需要去除的不需要的产物,然后才能进行任何进一步的下游处理。这项工作评估了通过气相部分氧化从合成气流中选择性去除碳氢化合物的潜力。具体来说,在环境压力下,在 760-910°C 的温度范围内和 0.4 至 2.4 s 的停留时间范围内,使用管式流动反应器研究了甲烷掺杂、乙烯掺杂和甲烷/乙烯掺杂模型合成气混合物的部分氧化。对于含有甲烷或乙烯的合成气混合物,添加氧气会大大降低碳氢化合物浓度,而氢浓度仅略有降低。对于掺杂有甲烷和乙烯的合成气混合物,添加氧气会优先去除乙烯,而甲烷和氢的浓度相对不受影响。将这些结果与使用旨在描述小分子烃类热解和部分氧化的反应机理的活塞流模型的预测进行了比较。实验观察结果与模型预测结果非常吻合,这使我们能够探索导致碳氢化合物选择性氧化的基础化学。根据使用合成气通过固体氧化物燃料电池生产液体燃料和电力的情况,简要讨论了这些结果的意义。