The literature treating mechanisms of catalyst deactivation is reviewed. Intrinsic mechanisms of catalyst deactivation are many; nevertheless, they can be classified into six distinct types: (i) poisoning, (ii) fouling, (iii) thermal degradation, (iv) vapor compound formation accompanied by transport, (v) vapor-solid and/or solid-solid reactions, and (vi) attrition/crushing. As (i), (iv), and (v) are chemical in nature and (ii) and (v) are mechanical, the causes of deactivation are basically three-fold: chemical, mechanical and thermal. Each of these six mechanisms is defined and its features are illustrated by data and examples from the literature. The status of knowledge and needs for further work are also summarized for each type of deactivation mechanism. The development during the past two decades of more sophisticated surface spectroscopies and powerful computer technologies provides opportunities for obtaining substantially better understanding of deactivation mechanisms and building this understanding into comprehensive mathematical models that will enable more effective design and optimization of processes involving deactivating catalysts. © 2001 Elsevier Science B.V. All rights reserved.

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Mechanisms of catalyst deactivation

Deactivation of heterogeneous catalysts is a ubiquitous problem that causes loss of catalytic rate with time. This review on deactivation and regeneration of heterogeneous catalysts classifies deactivation by type (chemical, thermal, and mechanical) and by mechanism (poisoning, fouling, thermal degradation, vapor formation, vapor-solid and solid-solid reactions, and attrition/crushing). The key features and considerations for each of these deactivation types is reviewed in detail with reference to the latest literature reports in these areas. Two case studies on the deactivation mechanisms of catalysts used for cobalt Fischer-Tropsch and selective catalytic reduction are considered to provide additional depth in the topics of sintering, coking, poisoning, and fouling. Regeneration considerations and options are also briefly discussed for each deactivation mechanism.

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Heterogeneous Catalyst Deactivation and Regeneration: A Review

A critical review of the kinetics and selectivity of the Fischer–Tropsch synthesis (FTS) is given. The focus is on reaction mechanisms and kinetics of the water–gas shift and Fischer–Tropsch (FT) reactions. New developments in the product selectivity as well as the overall kinetics are reviewed. It is concluded that the development of rate equations for the FTS should be based on realistic mechanistic schemes. Qualitatively, there is agreement that the product distribution is affected by the occurrence of secondary reactions (hydrogenation, isomerization, reinsertion, and hydrogenolysis). At high CO and H2O pressures, the most important secondary reaction is readsorption of olefins, resulting in initiation of chain growth processes. Secondary hydrogenation of α-olefins may occur and depends on the catalytic system and the process conditions. The rates of the secondary reactions increase exponentially with chain length. Much controversy exists about whether these chain-length dependencies stem from differe...

Kinetics and Selectivity of the Fischer–Tropsch Synthesis: A Literature Review

Lower olefins are key building blocks for the manufacture of plastics, cosmetics, and drugs. Traditionally, olefins with two to four carbons are produced by steam cracking of crude oil-derived naphtha, but there is a pressing need for alternative feedstocks and processes in view of supply limitations and of environmental issues. Although the Fischer-Tropsch synthesis has long offered a means to convert coal, biomass, and natural gas into hydrocarbon derivatives through the intermediacy of synthesis gas (a mixture of molecular hydrogen and carbon monoxide), selectivity toward lower olefins tends to be low. We report on the conversion of synthesis gas to C(2) through C(4) olefins with selectivity up to 60 weight percent, using catalysts that constitute iron nanoparticles (promoted by sulfur plus sodium) homogeneously dispersed on weakly interactive α-alumina or carbon nanofiber supports.

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Supported Iron Nanoparticles as Catalysts for Sustainable Production of Lower Olefins

http://pubs.acs.org/doi/pdfplus/10.1021/cr500486u

Recent Developments in the Synthesis of Supported Catalysts

Activation of Precipitated Iron Fischer-Tropsch Synthesis Catalysts

A precipitated, doubly promoted, iron oxide catalyst was studied to elucidate phenomena that may lead to catalyst attrition during slurry phase Fischer-Tropsch synthesis. The catalyst was examined by electron microscopy (SEM and TEM), electron and X-ray diffraction, sedigraph particle size analysis and BET surface area measurements. The catalyst undergoes attrition both at the micro- as well as the nano-length scales. On the micro-scale, this involves a breakup of ca. 30 μm spherical agglomerates into ca. 1 μm particles, a process that can be initiated even by the mixing that occurs in the sedigraph analyzer. On the nano-scale, we find that exposure of the catalyst to CO at increasing temperatures transforms single crystals of α-Fe 2 O 3 into Fe 3 O 4 and ultimately to Fe-carbide, with rounded particles as small as ca. 20 nm. The details of phase transformations and the resulting crystallite morphology and size distribution could play a major role in influencing the overall attrition resistance of precipitated iron oxide catalysts. In this paper, we describe the effects of the CO activation temperature on catalyst structure at the micro- and nano-scales.

Attrition of precipitated iron Fischer-Tropsch catalysts

Pure and mixed magnesium molybdate phases (MoO3, MgMoO4, and MgMo2O7) have been examined for the oxidative dehydrogenation reaction of propane. The results are very sensitive to the stoichiometry and method of preparation. The catalysts exhibiting superior activity and selectivity are characterized by a unique temperature-programmed reduction peak that is not present for the poorly active or selective catalysts. Mixtures of MgMoO4 and MoO3 or MgMoO4 and MgMo2O7, materials that perform poorly by themselves, show significant improvements in performance upon heating. The solid-state interactions leading to these improvements correspond to the appearance of the characteristic reduction peak. The results suggest that the beneficial synergistic effects seen with mixtures of inactive phases are due to formation of a new phase or species, rather than remote communication between phases (e.g., oxygen spillover).

The formation of active species for oxidative dehydrogenation of propane on magnesium molybdates

A number of different iron Fischer-Tropsch catalysts were characterized with an emphasis on the study of morphological changes of the iron and iron carbide, phases as well as the growth and morphology of carbon species during reaction. The effects of catalyst composition, reaction temperature, and pretreatment were investigated. Temperature programmed surface reaction of H 2 with a number of used catalysts revealed the formation of more than one carbide under certain circumstances. This paper considers deactivation and catalyst attrition for catalysts reacted in a slurry phase autoclave reactor. Several similar catalysts were tested for activity for long periods of time (1000–3000 h), and it was found that when operated properly, these iron Fischer-Tropsch catalysts can be run in slurry reactors with only modest deactivation, during the time periods tested.

Deactivation and attrition of iron catalysts in synthesis gas

Ethane oxidation reactions were studied over pure and Ca-, Mg-, Sr-, La-, Nd-, and Y-substituted BaCeO3 perovskites under oxygen limited conditions. Several of the materials, notably the Ca- and Y-substituted materials, show activity for complete oxidation of the hydrocarbon to CO2 at temperatures below 650°C. At higher temperatures, the oxidative dehydrogenation (ODH) to ethylene becomes significant. Conversions and ethylene yields are enhanced by the perovskites above the thermal reaction in our system in some cases. The perovskite structure is not retained in the high temperature reaction environment. Rather, a mixture of carbonates and oxides is formed. Loss of the perovskite structure correlates with a loss of activity and selectivity to ethylene.

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Nancy B. Jackson

Papers

Activation of Precipitated Iron Fischer-Tropsch Synthesis Catalysts

Attrition of precipitated iron Fischer-Tropsch catalysts

The formation of active species for oxidative dehydrogenation of propane on magnesium molybdates

Deactivation and attrition of iron catalysts in synthesis gas

Oxidation reactions of ethane over Ba–Ce–O based perovskites