Heptane Reforming over Pt–Re/Al2O3: Reaction Network, Kinetics, and Apparent Selective Catalyst Deactivation

2002 ◽  
Vol 206 (2) ◽  
pp. 188-201 ◽  
Author(s):  
K. Liu ◽  
S.C. Fung ◽  
T.C. Ho ◽  
D.S. Rumschitzki
Keyword(s):  
Catalyst Deactivation ◽  
Reaction Network ◽  
Selective Catalyst ◽  
Heptane Reforming

scholarly journals Analysis and Model-Based Description of the Total Process of Periodic Deactivation and Regeneration of a VOx Catalyst for Selective Dehydrogenation of Propane

Catalysts ◽  
2020 ◽  
Vol 10 (12) ◽  
pp. 1374
Author(s):  
Andreas Brune ◽  
Andreas Seidel-Morgenstern ◽  
Christof Hamel
Keyword(s):  
Catalyst Deactivation ◽  
Process Development ◽  
Coke Formation ◽  
Fixed Bed ◽  
Reaction Network ◽  
Fixed Bed Reactor ◽  
Side Reactions ◽  
Model Based ◽  
Total Process

This study intends to provide insights into various aspects related to the reaction kinetics of the VOx catalyzed propane dehydrogenation including main and side reactions and, in particular, catalyst deactivation and regeneration, which can be hardly found in combination in current literature. To kinetically describe the complex reaction network, a reduced model was fitted to lab scale experiments performed in a fixed bed reactor. Additionally, thermogravimetric analysis (TGA) was applied to investigate the coking behavior of the catalyst under defined conditions considering propane and propene as precursors for coke formation. Propene was identified to be the main coke precursor, which agrees with results of experiments using a segmented fixed bed reactor (FBR). A mechanistic multilayer-monolayer coke growth model was developed to mathematically describe the catalyst coking. Samples from long-term deactivation experiments in an FBR were used for regeneration experiments with oxygen to gasify the coke deposits in a TGA. A power law approach was able to describe the regeneration behavior well. Finally, the results of periodic experiments consisting of several deactivation and regeneration cycles verified the long-term stability of the catalyst and confirmed the validity of the derived and parametrized kinetic models for deactivation and regeneration, which will allow model-based process development and optimization.

Kinetic Modelling of Propane Dehydrogenation over a Pt–Sn/hierarchical SAPO-34 Zeolite Catalyst, Including Catalyst Deactivation

2017 ◽  
Vol 42 (4) ◽  
pp. 344-360
Author(s):  
Milad Komasi ◽  
Shohreh Fatemi ◽  
Seyed Hesam Mousavi
Keyword(s):  
Catalyst Deactivation ◽  
Kinetic Modelling ◽  
Coke Formation ◽  
Fixed Bed ◽  
Reaction Network ◽  
Normal Pressure ◽  
Fixed Bed Reactor ◽  
Propane Dehydrogenation ◽  
Coke Deposition ◽  
Formation Kinetic

Pt–Sn/hierarchical SAPO-34 was synthesised and kinetically modelled as an efficient and selective catalyst for propylene production through propane dehydrogenation. The kinetics of the reaction network were studied in an integral fixed-bed reactor at three temperatures of 550, 600 and 650 °C and weight hourly space velocities of 4 and 8 h−1 with a feed containing hydrogen and propane with relative molar ratios of 0.2, 0.5 and 0.8, at normal pressure. The experiments were performed in accordance with the full factorial experimental design. The kinetic models were constructed on the basis of different mechanisms and various deactivation models. The kinetics and deactivation parameters were simultaneously predicted and optimised using genetic algorithm optimisation. It was further proven that the Langmuir–Hinshelwood model can well predict propane dehydrogenation kinetics through lumping together all the possible dehydrogenation steps and also by assuming the surface reaction as the rate-determining step. A coke formation kinetic model has also shown appropriate results, confirming the experimental data by equal consideration of both monolayer and multilayer coke deposition kinetic orders and an exponential deactivation model.

What catalysis needs from the electron microscopist

1988 ◽  
Vol 46 ◽  
pp. 694-695
Author(s):  
Alexis T. Bell
Keyword(s):  
Active Sites ◽  
Heterogeneous Catalysts ◽  
Catalyst Deactivation ◽  
Surface Composition ◽  
Internal Surface ◽  
Active Phase ◽  
Atomic Scale ◽  
Metal Catalyst ◽  
Internal Surface Area ◽  
Porous Support

Heterogeneous catalysts, used in industry for the production of fuels and chemicals, are microporous solids characterized by a high internal surface area. The catalyticly active sites may occur at the surface of the bulk solid or of small crystallites deposited on a porous support. An example of the former case would be a zeolite, and of the latter, a supported metal catalyst. Since the activity and selectivity of a catalyst are known to be a function of surface composition and structure, it is highly desirable to characterize catalyst surfaces with atomic scale resolution. Where the active phase is dispersed on a support, it is also important to know the dispersion of the deposited phase, as well as its structural and compositional uniformity, the latter characteristics being particularly important in the case of multicomponent catalysts. Knowledge of the pore size and shape is also important, since these can influence the transport of reactants and products through a catalyst and the dynamics of catalyst deactivation.

Analytical Electron Microscopy study of two vehicle-aged automotive exhaust catalysts having dissimilar activities

1989 ◽  
Vol 47 ◽  
pp. 272-273
Author(s):  
Sooho Kim ◽  
M. J. D’Aniello
Keyword(s):  
Electron Microscopy ◽  
Particle Size ◽  
Noble Metal ◽  
Catalyst Deactivation ◽  
Analytical Electron Microscopy ◽  
Microscopy Study ◽  
Metal Particles ◽  
Automotive Exhaust ◽  
Exhaust Catalysts ◽  
Analytical Electron

Automotive catalysts generally lose-agtivity during vehicle operation due to several well-known deactivation mechanisms. To gain a more fundamental understanding of catalyst deactivation, the microscopic details of fresh and vehicle-aged commercial pelleted automotive exhaust catalysts containing Pt, Pd and Rh were studied by employing Analytical Electron Microscopy (AEM). Two different vehicle-aged samples containing similar poison levels but having different catalytic activities (denoted better and poorer) were selected for this study.The general microstructure of the supports and the noble metal particles of the two catalysts looks similar; the noble metal particles were generally found to be spherical and often faceted. However, the average noble metal particle size on the poorer catalyst (21 nm) was larger than that on the better catalyst (16 nm). These sizes represent a significant increase over that found on the fresh catalyst (8 nm). The activity of these catalysts decreases as the observed particle size increases.

An analytical microscopic study of metals in fluidized catalytic cracking catalyst

1986 ◽  
Vol 44 ◽  
pp. 854-855
Author(s):  
Clifford S. Rainey
Keyword(s):  
Electron Microscopy ◽  
Spatial Distribution ◽  
Catalytic Cracking ◽  
Catalyst Deactivation ◽  
Coke Formation ◽  
Acid Sites ◽  
Y Zeolite ◽  
Fcc Catalyst ◽  
Fluidized Catalytic Cracking ◽  
High Regeneration

The spatial distribution of V and Ni deposited within fluidized catalytic cracking (FCC) catalyst is studied because these metals contribute to catalyst deactivation. Y zeolite in FCC microspheres are high SiO2 aluminosilicates with molecular-sized channels that contain a mixture of lanthanoids. They must withstand high regeneration temperatures and retain acid sites needed for cracking of hydrocarbons, a process essential for efficient gasoline production. Zeolite in combination with V to form vanadates, or less diffusion in the channels due to coke formation, may deactivate catalyst. Other factors such as metal "skins", microsphere sintering, and attrition may also be involved. SEM of FCC fracture surfaces, AEM of Y zeolite, and electron microscopy of this work are developed to better understand and minimize catalyst deactivation.

Elucidating the Weakly Reversible Cs-Pb-Br Perovskite Nanocrystal Reaction Network with High-Throughput Maps and Transformations

2020 ◽  
Author(s):  
Jakob Dahl ◽  
Xingzhi Wang ◽  
Xiao Huang ◽  
Emory Chan ◽  
Paul Alivisatos
Keyword(s):  
High Throughput ◽  
Dynamic Equilibrium ◽  
Reaction Network ◽  
Substantial Impact ◽  
Equilibrium Behavior ◽  
Automated Method ◽  
Lead Bromide ◽  
Different Shapes ◽  
Complex Chemistry ◽  
Lead Halide

<p>Advances in automation and data analytics can aid exploration of the complex chemistry of nanoparticles. Lead halide perovskite colloidal nanocrystals provide an interesting proving ground: there are reports of many different phases and transformations, which has made it hard to form a coherent conceptual framework for their controlled formation through traditional methods. In this work, we systematically explore the portion of Cs-Pb-Br synthesis space in which many optically distinguishable species are formed using high-throughput robotic synthesis to understand their formation reactions. We deploy an automated method that allows us to determine the relative amount of absorbance that can be attributed to each species in order to create maps of the synthetic space. These in turn facilitate improved understanding of the interplay between kinetic and thermodynamic factors that underlie which combination of species are likely to be prevalent under a given set of conditions. Based on these maps, we test potential transformation routes between perovskite nanocrystals of different shapes and phases. We find that shape is determined kinetically, but many reactions between different phases show equilibrium behavior. We demonstrate a dynamic equilibrium between complexes, monolayers and nanocrystals of lead bromide, with substantial impact on the reaction outcomes. This allows us to construct a chemical reaction network that qualitatively explains our results as well as previous reports and can serve as a guide for those seeking to prepare a particular composition and shape. </p>

Synthesis and Breakdown of the Universal Precursors to Biological Metabolism Promoted by Ferrous Iron

2018 ◽  
Author(s):  
Kamila B. Muchowska ◽  
Sreejith Jayasree VARMA ◽  
Joseph Moran
Keyword(s):  
Amino Acids ◽  
Chemical Reaction ◽  
Metabolic Pathways ◽  
Ferrous Iron ◽  
Reaction Network ◽  
Tca Cycle ◽  
Chemical Reaction Network ◽  
Metabolic Precursors ◽  
Tca Cycle Intermediates

How core biological metabolism initiated and why it uses the intermediates, reactions and pathways that it does remains unclear. Life builds its molecules from CO<sub>2 </sub>and breaks them down to CO<sub>2 </sub>again through the intermediacy of just five metabolites that act as the hubs of biochemistry. Here, we describe a purely chemical reaction network promoted by Fe<sup>2+ </sup>in which aqueous pyruvate and glyoxylate, two products of abiotic CO<sub>2 </sub>reduction, build up nine of the eleven TCA cycle intermediates, including all five universal metabolic precursors. The intermediates simultaneously break down to CO<sub>2 </sub>in a life-like regime resembling biological anabolism and catabolism. Introduction of hydroxylamine and Fe<sup>0 </sup>produces four biological amino acids. The network significantly overlaps the TCA/rTCA and glyoxylate cycles and may represent a prebiotic precursor to these core metabolic pathways.

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