Transient Kinetic Experiments within the High Conversion Domain: The Case of Ammonia Decomposition

In the development of catalytic materials, a set of standard conditions is needed where the kinetic performance of many samples can be compared. This can be challenging when a sample set covers a broad range of activity. Precise kinetic characterization requires uniformity in the gas and catalyst be...

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Published in:Catalysts 2019-01, Vol.9 (1), p.104
Main Authors: Wang, Yixiao, Kunz, M., Siebers, Skyler, Rollins, Harry, Gleaves, John, Yablonsky, Gregory, Fushimi, Rebecca
Format: Article
Language:English
Subjects:
Advecting differential plug flow reactor
Ammonia
ammonia decomposition
Bimetals
Catalysts
Chemical elements
Chemical reactions
Cobalt
Composition
Conversion
Decomposition
Decomposition reactions
Experiments
Hydrogen production
Iron
MATERIALS SCIENCE
Microscopy
Nitrogen
PFR
Plug flow chemical reactors
TAP
TAP reactor
temporal analysis of products
Temporal Analysis of Products Reactor
Time dependence
transient kinetics
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container_issue 1
container_start_page 104
container_title Catalysts
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creator Wang, Yixiao
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Siebers, Skyler
Rollins, Harry
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Yablonsky, Gregory
Fushimi, Rebecca
description In the development of catalytic materials, a set of standard conditions is needed where the kinetic performance of many samples can be compared. This can be challenging when a sample set covers a broad range of activity. Precise kinetic characterization requires uniformity in the gas and catalyst bed composition. This limits the range of convecting devices to low conversion (generally
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This can be challenging when a sample set covers a broad range of activity. Precise kinetic characterization requires uniformity in the gas and catalyst bed composition. This limits the range of convecting devices to low conversion (generally &lt;20%). While steady-state kinetics offer a snapshot of conversion, yield and apparent rates of the slow reaction steps, transient techniques offer much greater detail of rate processes and hence more information as to why certain catalyst compositions offer better performance. In this work, transient experiments in two transport regimes are compared: an advecting differential plug flow reactor (PFR) and a pure-diffusion temporal analysis of products (TAP) reactor. The decomposition of ammonia was used as a model reaction to test three simple materials: polycrystalline iron, cobalt and a bimetallic preparation of the two. These materials presented a wide range of activity and it was not possible to capture transient information in the advecting device for all samples at the same conditions while ensuring uniformity. We push the boundary for the theoretical estimates of uniformity in the TAP device and find reliable kinetic measurement up to 90% conversion. However, what is more advantageous from this technique is the ability to observe the time-dependence of the reaction rate rather than just singular points of conversion and yield. For example, on the iron sample we observed reversible adsorption of ammonia and on cobalt materials we identify two routes for hydrogen production. From the time-dependence of reactants and product, the dynamic accumulation was calculated. This was used to understand the atomic distribution of H and N species regulated by the surface of different materials. When ammonia was pulsed at 550 °C, the surface hydrogen/nitrogen, (H/N), ratios that evolved for Fe, CoFe and Co were 2.4, 0.25 and 0.3 respectively. This indicates that iron will store a mixture of hydrogenated species while materials with cobalt will predominantly store NH and N. While much is already known about iron, cobalt and ammonia decomposition, the goal of this work was to demonstrate new tools for comparing materials over a wider window of conversion and with much greater kinetic detail. 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subjects Advecting differential plug flow reactor
Ammonia
ammonia decomposition
Bimetals
Catalysts
Chemical elements
Chemical reactions
Cobalt
Composition
Conversion
Decomposition
Decomposition reactions
Experiments
Hydrogen production
Iron
MATERIALS SCIENCE
Microscopy
Nitrogen
PFR
Plug flow chemical reactors
TAP
TAP reactor
temporal analysis of products
Temporal Analysis of Products Reactor
Time dependence
transient kinetics
title Transient Kinetic Experiments within the High Conversion Domain: The Case of Ammonia Decomposition
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