New Reaction Engineering Concepts for Selective Oxidation Reactions

In order to enhance product yields in selective oxidation reactions, numerous reaction engineering concepts are being studied worldwide. Periodic operation has been investigated for decades, yet its application is limited to a few examples, such as the butane oxidation after DuPont or reverse-flow reactors for VOC removal. The use of microchannel reactors is a younger field, but it has already yielded promising results for process optimization. Catalytic wall reactors have proved to be a helpful tool for kinetic studies. On the laboratory scale, membrane reactors have displayed favorable behavior in selective oxidation. The Na vapor-catalyzed dehydrogenation of methanol to formaldehyde is a final example of an unusual new concept for selective oxidation.     

Hydrogen production in solid electrolyte membrane reactors (SEMRs)

In the present work, the prospects and trends of solid electrolyte membrane reactors (SEMRs) towards hydrogen production, are discussed. Initially, an overview of the principles, the properties and the techniques related to the usage of the SEMRs, are presented. In the following, a literature survey covering earlier and recent developments of the various methods (e.g. reforming or partial oxidation or dehydrogenation of hydrocarbons, steam electrolysis) employed in the SEMRs for the production of hydrogen, is performed. Finally, the current status of this research field is analyzed and future research topics are proposed.     

Hydrogen production in solar reactors

The present work summarizes the recent activities of our laboratory in the field of solar-aided hydrogen production with structured monolithic solar reactors. This reactor concept, “transferred” from the well-known automobile exhaust catalytic after-treatment systems, employs ceramic supports optimized to absorb effectively solar radiation and develop sufficiently high temperatures, that are coated with active materials capable to perform/catalyze a variety of “solar-aided” reactions for the production of hydrogen such as water splitting or natural gas reforming. Our work evolves in an integrated approach starting from the synthesis of active powders tailored to particular hydrogen production reactions, their deposition upon porous absorbers, testing of relevant properties of merit such as thermomechanical stability and hydrogen yield and finally to the design, operation simulation and performance optimization of structured monolithic solar hydrogen production reactors. This approach, among other things, has culminated to the world's first closed, solar-thermochemical cycle in operation that is capable of continuous hydrogen production employing entirely renewable and abundant energy sources and raw materials – solar energy and water, respectively – without any CO₂ emissions and holds, thus, a significant potential for large-scale, emissions-free hydrogen production, particularly for regions of the world that lack indigenous resources but are endowed with ample solar energy.     

Stationary and traveling hot spots in the catalytic combustion of hydrogen in monoliths

In the course of catalytic combustion of hydrogen (1-5% H₂ in air) in monolith reactors, strongly localized stationary and traveling hot spots arise in response to a sudden and persistent rise of gas flow velocity. Such hot spots may occur, e.g. in a catalytic converter following the acceleration of a car or in a catalytic combustor as a result of a load increase. This phenomenon is illustrated by simulations using a two-phase reactor model. The temperature overshoot of the adiabatic limit is typically of the order of the adiabatic temperature rise itself.The following mechanism underlies this behavior. Light fuel is supplied to the catalytic wall by fast diffusion (in the direction perpendicular to flow), while the heat released by reaction is removed from the wall by the slower, mixture-averaged heat conduction. This leads to accumulation of heat at the catalytic surface that eventually saturates at high temperatures. The hot spots may exhibit intricate dynamics, propagating downstream or upstream, or they may remain stationary. The direction of propagation depends on the relative strength of convective downstream and conductive upstream contributions to the overall displacement of reaction fronts. Generally, the hot spot tends to drift downstream at low flow velocities, remain stationary at intermediate flow velocities, and drift upstream at high flow velocities.     

Danckwerts’ law for mean residence time revisited

This paper shows that Danckwerts’ law for mean residence time in a vessel with continuous and steady throughflow holds for a stochastic model based on a Markov chain for the particle spatial position, under a set of three very general conditions on the transfer probabilities. These are natural conditions and represent mass balance conditions on the transfer between spatial regions in the process. It is shown that a stochastic model for particle residence time distribution with these three conditions may describe almost any physical flow configuration, and also covers published mathematical RTD models, independent of their mathematical form or the nature of the associated boundary conditions, models for which Danckwert's law has hitherto been shown to be satisfied on a case-by-case basis. Two examples, namely those birth-death Markov chains and fluidized bed models are discussed.     

Adaptation of the microscopic properties of redox catalysts to the type of gas-solid reactor

Catalysts of selective oxidation usually work in a simultaneous redox mode in reactant/air cofed reactors. The solid must provide selective lattice oxygen according to a kinetic mechanism depending on operating conditions that differ from one reactor to another. Better catalytic performance can be obtained in a recirculating solids reactor because it allows separate optimization of the reduction and oxidation steps. Among the microscopic properties of the catalyst, the crystal morphology is to be taken into account because it influences its reactivity on stream. These considerations lead to a new approach of the catalyst-reaction-reactor trio.     

Symmetry properties and bifurcation analysis of a class of periodically forced chemical reactors

In this work, we discuss how periodic forcing may induce symmetry properties into mathematical models of chemical reactors. We define a class of reactors subjected to discontinuous periodic forcing, and show that all the reactors belonging to this class have spatio-temporal symmetry. This symmetry and its influence on the possible bifurcation scenarios are discussed. The bifurcation analysis is carried out with suitable discrete systems that exploit a property of the Poincaré map. In fact, it is shown that the spatio-temporal symmetry induced by the forcing makes the Poincaré map of the continuous system an iterate of another map. On this basis, a technique to implement parameter continuation methods is proposed. With such a technique, it is also possible to characterize symmetric and nonsymmetric regimes and unstable limit sets otherwise undetected with “bruteforce” approaches. Examples for reverseflow reactors and networks of n-reactors with periodically switched feed and discharge positions are presented.     

Modelling of addition polymerization processes — Free radical,ionic, group transfer,and ziegler–natta kinetics

A brief review of addition polymerization processes is presented with a summary of the key characteristics classified by kinetic mechanism (free-radical, anionic, cationic, group transfer, or Ziegler–Natta), phase behavior, and reactor type. A practical approach to modelling in the industrial R & D environment is discussed in terms of a CAD package for polymerization processes.