Rapid extraction of quantitative kinetic information from variable-temperature reaction profiles

• Analytical equations describe variable-temperature reaction (activity) profiles in packed-bed reactors (PBR).
• Simulated reaction profiles reproduce key features of experimental profiles that are free of mass and heat transfer effects.
• The influence of individual reaction parameters on the variable-temperature reaction profiles is demonstrated.
• Non-linear curve-fitting of variable-temperature profiles can yield accurate kinetic parameters.
• The method is demonstrated for the oxidation of CO, H2, and C3H8 by O2 catalyzed by Pd/Al2O3.

Analysis of variable-temperature reaction profiles, measured in an isothermal packed-bed reactor (PBR) whose temperature increases during the experiment, has the potential to yield accurate and precise kinetic parameters quickly for some heterogeneous catalysts. The method is demonstrated here for a typical supported nanoparticle catalyst, 2 wt% Pd/Al2O3, in the oxidation of H2, C3H8 and CO by O2. These reactions do not exhibit major changes in activation energy as a function of conversion over the range of reaction conditions analyzed. Reliable and quantitative information about rate laws was extracted readily from the shapes and positions of the profiles, as an alternative to more laborious conventional kinetic analyses. Temperature and pressure gradients were minimized by the use of sieved catalyst particles and large amounts of inert diluent for both the catalyst and feed gas. Curve-fitting of analytical expressions with as few as two adjustable parameters results in remarkable agreement between models and data. First-order profiles are kinetically-limited, without mass and heat transfer effects, while inverse-first-order profiles deviate from kinetically-controlled behavior at intermediate-to-high conversions. The activation energy and reaction order with respect to the limiting reactant obtained from a single reaction profile (with appropriate data truncation for non-kinetic phenomena, as necessary) are at least as accurate and precise as those obtained from a conventional Arrhenius analysis conducted with data obtained under differential conditions, and can be measured in a fraction of the experimental time. Information about more elaborate rate laws can be obtained by global curve-fitting of a family of such profiles recorded with different volumetric flow rates.

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