Axial Changes of Catalyst Structure and Temperature in a Fixed-Bed Microreactor During Noble Metal Catalysed Partial Oxidation of Methane

摘要

The catalytic partial oxidation of methane (CPO) over flame-made 2.5%Rh-2.5%Pt/Al2O3 and 2.5%Rh/Al2O3 in 6%CH4/3%O-2/He shows the potential of in situ studies using miniaturized fixed-bed reactors, the importance of spatially resolved studies and its combination with infrared thermography and on-line mass spectrometry. This experimental strategy allowed collecting data on the structure of the noble metal (oxidation state) and the temperature along the catalyst bed. The reaction was investigated in a fixed-bed quartz microreactor (1-1.5 mm diameter) following the catalytic performance by on-line gas mass spectrometry (MS). Above the ignition temperature of the catalytic partial oxidation of methane (310-330 A degrees C), a zone with oxidized noble metals was observed in the inlet region of the catalyst bed, accompanied by a characteristic hot spot (over-temperature up to 150 A degrees C), while reduced noble metal species became dominant towards the outlet of the bed. The position of both the gradient in oxidation state and the hot spot were strongly dependent on the furnace temperature and the gas flow (residence time). Heating as well as a higher flow rate caused a migration of the transition zone of the oxidation state/maximum in temperature towards the inlet. At the same time the hydrogen concentration in the reactor effluent increased. In contrast, at low temperatures a movement of the transition zone towards the outlet was observed at increasing flux, except if the self-heating by the exothermic methane oxidation was too strong. The results indicate that in the oxidized zone mainly combustion of methane occurs, whereas in the reduced part direct partial oxidation and reforming reactions prevail. The results demonstrate how spatially resolved spectroscopy can help in understanding catalytic reactions involving different reaction zones and gradients even in micro scale fixed-bed reactors.