Olaf Deutschmann

Modeling Elementary Heterogeneous Chemistry and Electrochemistry in Solid-Oxide Fuel Cells

This paper presents a new computational framework for modeling chemically reacting flow in anode-supported solid-oxide fuel cells (SOFC). Depending on materials and operating conditions, SOFC anodes afford a possibility for internal reforming or catalytic partial oxidation of hydrocarbon fuels. An important new element of the model is the capability to represent elementary heterogeneous chemical kinetics in the form of multistep reaction mechanisms. Porous-media transport in the electrodes is represented with a dusty-gas model. Charge-transfer chemistry is represented in a modified Butler-Volmer setting that is derived from elementary reactions, but assuming a single rate-limiting step. The model is discussed in terms of systems with defined flow channels and planar membrane-electrode assemblies. However, the underlying theory is independent of the particular geometry. Examples are given to illustrate the model.

Hydrogen assisted catalytic combustion of methane on platinum

The objective of this paper is to study hydrogen assisted catalytic combustion of methane on platinum experimentally and numerically. In the experiment, we measure the exit temperatures of methane/hydrogen/air mixtures flowing at atmospheric pressure through platinum coated honeycomb channels. A single channel of this monolith is investigated numerically by a two-dimensional Navier-Stokes simulation including an elementary-step surface reaction mechanism. Furthermore, a one-dimensional time-dependent simulation of a stagnation flow configuration is performed to elucidate the elementary processes occurring during catalytic ignition in the mixtures studied. The dependence of the hydrogen assisted light-off of methane on hydrogen and on methane concentrations is discussed. The light-off is primarily determined by the catalyst temperature that is a result of the heat release due to catalytic hydrogen oxidation. Increasing hydrogen addition ensures light-off, decreasing hydrogen addition requires an increasing methane feed for light-off.

NUMERICAL MODELING OF CATALYTIC IGNITION

Catalytic ignition of CH4, CO, and H2 oxidation on platinum and palladium at atmospheric pressure is studied numerically. Two simple configurations are simulated: the stagnation flow field over a catalytically active foil and a chemical reactor with a catalytically active wire inside. The simulation includes detailed reaction mechanisms for the gas phase and for the surface. The gas-phase transport and its coupling to the surface is described using a simplified multicomponent model. The catalyst is characterized by its temperature and its coverage by adsorbed species. The dependence of the ignition temperature on the fuel/oxygen ratio is calculated and compared with experimental results. The ignition temperature of CH4 oxidation decreases with increasing CH4/O2 ratio, whereas the ignition temperature for the oxidation of H2 and CO increases with increasing fuel/oxygen ratio. The kinetic data for adsorption and desorption are found to be critical for the ignition process. They determine the dependence of the ignition temperature on the fuel/oxygen ratio. A sensitivity analysis leads to the rate-determining steps of the surface reaction mechanism. The bistable ignition behavior observed experimentally for lean H2/O2 mixtures on palladium is reproduced numerically. The abrupt transition from a kinetically controlled system before ignition to one controlled by mass transport after ignition is described by the time-dependent codes applied.

Experimental and numerical study on the transient behavior of partial oxidation of methane in a catalytic monolith

The objective of this investigation is a better understanding of transient processes in catalytic monoliths. As an example, the light-off of the partial oxidation of methane to synthesis gas (H2 and CO) on a rhodium/alumina catalyst is studied experimentally and numerically. Methane/oxygen/argon mixtures are fed at room temperature and atmospheric pressure into a honeycomb monolith, which is preheated until ignition occurs. The exit gas-phase temperature and species concentrations are monitored by a thermocouple and mass spectroscopy, respectively. In the numerical study, the time-dependent temperature distribution of the entire solid monolith structure and the two-dimensional laminar reactive flow fields in the single monolith channels are simulated. A multi-step heterogeneous reaction mechanism is used, and the surface coverage with adsorbed species is calculated as function of the position in the monolith. During light-off, complete oxidation of methane to water and carbon dioxide occurs initially. Then, synthesis gas selectivity slowly increases with rising temperature.

A critical evaluation of Navier–Stokes, boundary-layer, and plug-flow models of the flow and chemistry in a catalytic-combustion monolith

Abstract The objective of this paper is to evaluate three alternative formulations for simulating the steady-state flow and chemistry in a honeycomb channel for conditions that are typical of the catalytic combustion of natural gas. In developing simulation capabilities, it is important to understand the physical and computational accuracy that a model can deliver and the computational resources required to do so. Direct comparison of the solutions, using three different model formulations, reveal the range of validity of the various approximations. Computation times range from hours for the Navier–Stokes formulation to seconds for the plug-flow models.

Detailed surface reaction mechanism in a three-way catalyst

Monolithic three-way catalysts are applied to reduce the emission of combustion engines. The design of such a catalytic converter is a complex process involving the optimization of different physical and chemical parameters (in the simplest case, e.g., length, cell densities or metal coverage of the catalyst). Numerical simulation can be used as an effective tool for the investigation of the catalytic properties of a catalytic converter and for the prediction of the performance of the catalyst. To attain this goal, a two-dimensional flow-field description is coupled with a detailed surface reaction model (gas-phase reactions can be neglected in three-way catalysts). This surface reaction mechanism (with C3H6 taken as representative of unburnt hydrocarbons) was developed using sub-mechanisms recently developed for hydrogen, carbon monoxide and methane oxidation, literature values for C3H6 oxidation, and estimates for the remaining unknown reactions. Results of the simulation of a monolithic single channel are used to validate the surface reaction mechanism. The performance of the catalyst was simulated under lean, nearly stoichiometric and rich conditions. For these characteristic conditions, the oxidation of propene and carbon monoxide and the reduction of NO on a typical Pt/Rh coated three-way catalyst were simulated as a function of temperature. The numerically predicted conversion data are compared with experimentally measured data. The simulation further reveals the coupling between chemical reactions and transport processes within the monolithic channel.

Modelling and simulation of heterogeneous oxidation of methane on a platinum foil

Abstract The heterogeneous oxidation of methane-air mixtures in a stagnation point flow onto a platinum foil is investigated numerically and results are compared with experiments. The analysis includes a detailed reaction mechanism in the gas phase as well as on the surface. The heterogeneous ignition occurring around 600°C, extinction, and autothermal behaviour are interpreted in terms of elementary steps at the gas-surface interface.

Analysis of the Injection of Urea-Water-Solution for Automotive SCR DeNOx-Systems: Modeling of Two-Phase Flow and Spray/Wall-Interaction

The selective catalytic reduction (SCR) based on ureawater-solution is an effective technique to reduce nitrogen oxides (NOx) emitted from diesel engines. A 3D numerical computer model of the injection of urea-water-solution and their interaction with the exhaust gas flow and exhaust tubing is developed to evaluate different configurations during the development process of such a DeNOxsystem. The model accounts for all relevant processes appearing from the injection point to the entrance of the SCR-catalyst:

Extinction limits of catalytic combustion in microchannels

The limits to self-sustaining catalytic combustion in a microscale channel were studied computationally using a cylindrical tube reactor. The tube, 1 mm in diameter, 10 mm long, and coated with Pt catalyst, was assumed to be thermally thin, and the boundary condition on the wall was set to be either adiabatic or non-adiabatic with fixed heat transfer coefficient. Methane/air mixtures with average velocities of 0.0375–0.96 m/s (corresponding to Reynolds number, Re, ranging from 2.5 to 60) were used. When the wall boundary condition was adiabatic, the equivalence ratio at the extinction limit monotonically decreased with increasing Re. In contrast, for non-adiabatic conditions, the extinction curve exhibited U-shaped dual limit behavior, that is, the extinction limits increased/decreased with decreasing Re in smaller/larger Re regions, respectively. The former extinction limit is caused by heat loss through the wall, and the latter is a blow-off-type extinction due to insufficient residence time compared to the chemical timescale. These heat-losses and blow-off-type extinction limits are characterized by small/large surface coverage of Pt(s) and conversely large/small numbers of surface coverage of O(s). It was found that by diluting the mixture with N2 rather than air, the fuel concentration and peak temperatures at the limit decreased substantially for mixtures with fuel-to-oxygen ratios even slightly rich of stoichiometric because of a transition from O(s) coverage to CO(s) coverage. Analogous behavior was observed experimentally in a heat-recirculating “Swiss-roll” burner at low Re, suggesting that the phenomenon is commonplace in catalytic combustors near extinction. No corresponding behavior was found for non-catalytic combustion. These results suggest that exhaust-gas recirculation rather than lean mixtures are preferable for minimizing flame temperatures in catalytic microcombustors.

Transient three-dimensional simulations of a catalytic combustion monolith using detailed models for heterogeneous and homogeneous reactions and transport phenomena

Abstract The application of a newly developed computational tool, DETCHEMMONOLITH, for the transient two- and three-dimensional simulation of catalytic combustion monoliths is presented. The simulation is based on the coupling of a transient 2D/3D heat balance of the solid monolith structure with steady-state calculations of the reactive flow in a representative number of channels. The two-dimensional single-channel model uses a boundary-layer approximation including detailed models for heterogeneous and homogeneous reactions as well as transport phenomena. As an example, the computational tool is applied to study the hydrogen-assisted catalytic combustion of methane in a platinum-coated honeycomb monolith.