ABSTRACT
Catalytic partial oxidation of methane (POM) to synthesis gas (syngas) over Pt/Al(2)O(3) was investigated by in situ microprobe Raman and pulse reaction methods with attention focused on the mechanism of syngas formation in the oxidation zone (i.e., the catalyst zone in which O(2) was still available in the reaction feed). It was found that the amount of platinum oxide in the catalyst under POM conditions was below the detection level of Raman spectroscopy. Raman bands of carbon species that originated from methane dissociation were detected at the entrance of the catalyst bed under working conditions. The results of the pulse reaction study on POM as well as steam and CO(2) reforming of methane at 700 °C with a contact time of less than 1 ms over the catalyst suggest that pyrolysis of methane on reduced platinum sites followed by coupling of two surface hydrogen atoms to H(2) and partial oxidation of surface carbon species to CO are the major reactions responsible for syngas formation in the oxidation zone. Under the experimental conditions, steam and CO(2) reforming of methane play only a minor role in syngas formation in the same reaction zone. The contribution of the last two reactions increases with increasing contact time.