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

Steam reforming reactions will play a key role in new applications of synthesis gas and in a future hydrogen economy. The aim of this review is to provide a coherent description of the catalysis of the reforming reactions. The review is not comprehensive. The first section deals with the applications of synthesis gas and hydrogen and the various synthesis gas technologies. The optimum choice of technology depends on the requirements of the gas composition and the scale of operation. Two examples are included for illustration: synthesis gas for gas-to-liquid plants and hydrogen for fuel cells. The steam reforming process is described in the second section with emphasis on the role of the catalyst and problems related to carbon formation. The third section is a summary of the empirical evidence of the catalysis of the reforming reactions. The methods of characterization are discussed, and data representing sintering, activity trends, and promotion are summarized. The fourth section is a description of the mechanism based on a combination of empirical knowledge with recent data from studies of well-defined surfaces, in-situ high-resolution electron microscopy, and calculations based on density functional theory. The central concept is the role of surface defects as the source of reactivity and the nucleation centers for whisker carbon formation.

Hydrogen and Synthesis gas by Steam- and CO2 reforming

The steam reforming process converts hydrocarbons into mixtures of hydrogen, carbon monoxide, carbon dioxide, and methane 

$$C_n H_m + nH_2 O \to nCO + \left( {n + \frac{m}{2}} \right)H_2 \left( { - \Delta H_{298}^0 < 0} \right) $$

(1)



$$ CO + H_2 O \rightleftarrows CO_2 + H_2 \left( { - \Delta H_{298}^0 = 41.2kJ\,mol^{ - 1} } \right) $$

(2)



$$ CO + 3H_2 \rightleftarrows CH_4 + H_2 O\left( { - \Delta H_{298}^0 = 206.2kJ\,mol^{ - 1} } \right) $$

(3)

The expression reforming is misleading since it is used also for the well-knowm process for improvement of the octane number of gasoline [1]. In the gas industry, reforming has generally been used for “the changing by heat treatment of a hydrocarbon with high heating value into a gaseous mixture of lower heating value” [2].

Catalytic Steam Reforming

The stoichiometries of H2 and CO adsorptions on cobalt: Effects of support and preparation

The stoichiometry and poisoning by sulfur of hydrogen, oxygen and carbon monoxide chemisorption on unsupported nickel

Optimum coating thickness for the fastest chilldown of Teflon-coated stainless steel flat plate in liquid nitrogen pool

According to the regulation on the pollution of the marine environment, SOx emission from ships has to be reduced. A SOx scrubbing system installed in a funnel of a ship is considered in order to reduce SOx emission. A scrubbing layer with a porous material is present in the funnel to increase the contact area between exhaust gas and water. In this study, experiments on the pressure drop characteristics in the scrubbing layer are conducted to investigate the effect of the scrubber on the engine load. The pressure drop according to flow rate of air instead of exhaust gas was measured for fillers such as sphere, pall ring and saddle in the scrubbing layer. First of all, porosity is experimentally measured for the three types of filler and it is confirmed that the porosity of the saddle-type filler was the largest. The pressure drop according to the change in air flow rate was measured for the three types of fillers in the scrubbing layer. As a result, the pressure drop was the smallest in the scrubbing layer with the saddle-type filler which has the largest porosity. In addition, the effect of spraying water flowing counter flow against air flow is experimentally examined. It is known that the pressure drop is increased because the air flow space is reduced when water is sprayed. In the case of the saddle, the pressure drop is about 1.5 to 2 times greater than that when only air flows at the optimum exhaust gas-water injection ratio. 

Kyung Sup Chung

Papers

The stoichiometry and poisoning by sulfur of hydrogen, oxygen and carbon monoxide chemisorption on unsupported nickel

Optimum coating thickness for the fastest chilldown of Teflon-coated stainless steel flat plate in liquid nitrogen pool

Experiments for Pressure Drop of Scrubbing Layer in a Scrubber System