Experimental Method for Kinetic Studies of Gas鈥揝olid Reactions: Oxidation of Carbonaceous Matter

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• 作者：Carolin Wang-Hansen ; Carl J. Kamp ; Magnus Skoglundh ; Bengt Andersson ; Per-Anders Carlsson
• 刊名：Journal of Physical Chemistry C
• 出版年：2011
• 出版时间：August 18, 2011
• 年：2011
• 卷：115
• 期：32
• 页码：16098-16108
• 全文大小：1046K
• 年卷期：v.115,no.32(August 18, 2011)
• ISSN：1932-7455

文摘

A methodology comprising careful consideration of sample preparation, reactor design, experimental procedures, and data evaluation routines for precise analysis of the kinetics of gas鈥搒olid reactions, specifically the oxidation of carbonaceous materials, has been developed and validated. The well-controlled solvent-free deposition of the carbonaceous material onto cordierite monolith substrates ensures experimental studies in the absence of diffusion limitations, temperature gradients, and hot zones. These critical aspects are supported also by theoretical considerations. Temperature-programmed oxidation and isothermal oxygen step-response experiments in a continuous gas-flow reactor using a homogeneous synthetic carbon-black material demonstrate excellent reproducibility, and the conversion profiles agree well with previously reported data. An independent set of global kinetic parameters was estimated for each 5% subconversion interval using linear regression such that the conversion dependence of each parameter could be analyzed separately and compared to previously published data. The results show that the evolution of reactive carbons cannot be described with a single global reaction order. This is supported by intermittent ex situ measurements of the specific surface area of the carbon-black material during the course of isothermal oxidation, which reveals a developing microporous structure at high conversions. Physically the changes in carbon reaction order are interpreted as changes in fraction of accessible reactive carbon atoms during progressing oxidation. Moreover, at high conversions, the carbon reaction order approaches 0.7 implying not only that the evolution of the concentration of reactive carbon atoms is proportional to the external surface area of shrinking spheres but also that these spheres have approximately the same size.