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

Ultrasound assisted extraction of food and natural products. Mechanisms, techniques, combinations, protocols and applications. A review.

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 one-dimensional dual-porosity model has been developed for the purpose of studying variably saturated water flow and solute transport in structured soils or fractured rocks. The model involves two overlaying continua at the macroscopic level: a macropore or fracture pore system and a less permeable matrix pore system. Water in both pore systems is assumed to be mobile. Variably saturated water flow in the matrix as well as in the fracture pore system is described with the Richards' equation, and solute transport is described with the convection-dispersion equation. Transfer of water and solutes between the two pore regions is simulated by means of first-order rate equations. The mass transfer term for solute transport includes both convective and diffusive components. The formulation leads to two coupled systems of nonlinear partial differential equations which were solved numerically using the Galerkin finite element method. Simulation results demonstrate the complicated nature of solute leaching in structured, unsaturated porous media during transient water flow. Sensitivity studies show the importance of having accurate estimates of the hydraulic conductivity near the surface of soil aggregates or rock matrix blocks. The proposed model is capable of simulating preferential flow situations using parameters which can be related to physical and chemical properties of the medium.

A dual-porosity model for simulating the preferential movement of water and solutes in structured porous media

http://www.pc-progress.com/Documents/Jirka/Simunek_et_al_MacroFl_2002.pdf

Review and comparison of models for describing non-equilibrium and preferential flow and transport in the vadose zone

Ultrasonic fragmentation of agglomerate powders

Groundwater flow in unsaturated, fractured rock is often assumed to be dominated by the porous matrix component. This is frequently the result of reasoning that water flowing in the fractures is rapidly imbibed into the rock matrix by capillary suction forces with negligible resistance to uptake at the fracture/matrix interface. However, the existence of a low-permeability mineralized layer or coating at this interface may substantially reduce matrix imbibition and could consequently result in fracture-dominated flow. To test this idea, four tuff samples containing natural fractures were obtained from tuff formations in southern Nevada. By performing imbibition experiments into the matrix rock, across a mineralized fracture face and then across a fresh uncoated fracture face, water uptake as a function of time and coating was measured. A model combining Darcy's law and the Washburn equation has been used to describe the imbibition behavior. Before testing the tuff samples, the experimental technique and imbibition model were first tested using ordered sphere packings with known pore size and structure. From the tuff imbibition data, the ratio of the permeability through the mineralized face to the permeability through the uncoated face was found to be 0.3 (relatively little effect of the mineralized layer) for two samples, 0.01 for one sample, and 10−7 (uptake strongly restricted by the mineralized layer) for one sample. Using a simple fracture flow model and the imbibition model mentioned above to simulate matrix uptake from the fracture, numerical simulations indicate that the existence of fracture coatings could significantly decrease the travel time and increase the travel depth of water flowing through fractures.

Steven G. Thoma

Papers

Ultrasonic fragmentation of agglomerate powders

Impact of fracture coatings on fracture/matrix flow interactions in unsaturated, porous media

Energy—size reduction laws for ultrasonic fragmentation

Determination of agglomerate strength distributions

Determination of agglomerate strength distributions Part 3. Application to titania processing