Experimental and numerical investigation of hetero-/homogeneous combustion of CO/H2/O2/N2 mixtures over platinum at pressures up to 5 bar

The hetero-/homogeneous combustion of fuel-lean CO/H₂/O₂/N₂ mixtures over platinum is investigated at pressures up to 5 bar, inlet temperatures (T_IN) up to 874 K, and a constant CO:H₂ molar ratio of 2:1. Experiments are performed in an optically accessible channel-flow catalytic reactor and involve planar laser induced fluorescence (LIF) of the OH radical for the assessment of homogeneous (gas-phase) ignition and 1-D Raman measurements of major gas-phase species concentrations over the catalyst boundary layer for the evaluation of the heterogeneous (catalytic) processes. Simulations are carried out with an elliptic 2-D model that includes detailed heterogeneous and homogeneous chemical reaction schemes. The predictions reproduce the Raman-measured catalytic CO and H₂ consumption, and it is further shown that for wall temperatures in the range 975 ? T_w ? 1165 K the heterogeneous pathways of CO and H₂ are largely decoupled. However, for wall temperatures below a limiting value of 710–720 K and for the range of pressures and mixture preheats investigated, CO(s) blockage of the surface inhibits the catalytic conversion of both fuel components. The homogeneous ignition distance is well-reproduced by the model for T_IN > 426 K, but it is modestly overpredicted at lower T_IN. Possible reasons for these modest differences can be the values of third body efficiencies in the gas-phase reaction mechanism. The sensitivity of homogeneous ignition distance on the catalytic reactions is weak, while the H₂/O₂ subset of the CO/H₂/O₂ gaseous reaction mechanism controls the onset of homogeneous ignition. Pure hydrogen hetero-/homogeneous combustion results in flames established very close to the catalytic walls. However, in the presence of CO the gaseous combustion of hydrogen extends well-inside the channel core, thus allowing homogeneous consumption of H₂ at considerably shorter reactor lengths. Finally, implications of the above findings for the design of syngas-based catalytic reactors for power generation systems are discussed.     

Hetero-/homogeneous combustion of ethane/air mixtures over platinum at pressures up to 14 bar

The hetero-/homogeneous combustion of fuel-lean ethane/air mixtures over platinum was investigated experimentally and numerically at pressures of 1–14 bar, equivalence ratios of 0.1–0.5, and surface temperatures ranging from 700 to 1300 K. Experiments were carried out in an optically accessible channel-flow reactor and included in situ 1-D Raman measurements of major gas phase species concentrations across the channel boundary layer for determining the catalytic reactivity, and planar laser induced fluorescence (LIF) of the OH radical for assessing homogeneous ignition. Numerical simulations were performed with a 2-D CFD code with detailed hetero-/homogeneous C₂ kinetic mechanisms and transport. An appropriately amended heterogeneous reaction scheme has been proposed, which captured the increase of ethane catalytic reactivity with rising pressure. This scheme, when coupled to a gas-phase reaction mechanism, reproduced the combustion processes over the reactor extent whereby both heterogeneous and homogeneous reactions were significant and moreover, provided good agreement to the measured homogeneous ignition locations. The validated hetero-/homogeneous kinetic schemes were suitable for modeling the catalytic combustion of ethane at elevated pressures and temperatures relevant to either microreactors or large-scale gas turbine reactors in power generation systems. It was further shown that the pressure dependence of the ethane catalytic reactivity was substantially stronger compared to that of methane, at temperatures up to 1000 K. Implications for high-pressure catalytic combustion of natural gas were finally drawn.     

Experimental and numerical investigation of the hetero-/homogeneous combustion of lean propane/air mixtures over platinum

The pure heterogeneous and the coupled hetero-/homogeneous combustion of fuel-lean propane/air mixtures over platinum have been investigated at pressures 1 bar  p  7 bar, fuel-to-air equivalence ratios 0.23  φ  0.43, and catalytic wall temperatures 723 K  T_w  1286 K. Experiments were performed in an optically accessible catalytic channel-flow reactor and involved 1-D Raman measurements of major gas-phase species concentrations across the reactor boundary layer for the assessment of catalytic fuel conversion and planar laser induced fluorescence (LIF) of the OH radical for the determination of homogeneous ignition. Numerical predictions were carried out with a 2-D elliptic CFD code that included a one-step catalytic reaction for the total oxidation of propane on Pt, an elementary C₃ gas-phase chemical reaction mechanism, and detailed transport. A global catalytic reaction step valid over the entire pressure–temperature-equivalence ratio parameter range has been established, which revealed a p^0.75 dependence of the catalytic reactivity on pressure. The aforementioned global catalytic step was further coupled to a detailed gas-phase reaction mechanism in order to simulate homogeneous ignition characteristics in the channel-flow reactor. The predictions reproduced within 10% the measured homogeneous ignition distances at pressures p  5 bar, while at p = 7 bar the simulations overpredicted the measurements by 19%. The overall model performance suggests that the employed hetero-/homogeneous chemical reaction schemes are suitable for the design of propane-fueled catalytic microreactors.     

Transient simulation of the combustion of fuel-lean hydrogen/air mixtures in platinum-coated channels

The start-up of platinum-coated, hydrogen-fuelled planar channels with heights of 1 mm is investigated numerically using 2-D transient simulations with detailed hetero-/homogeneous chemistry, heat conduction in the solid wall and surface radiation heat transfer. Simulations encompass pressures of 1 and 5 bar and fuel-lean H₂/air equivalence ratios of 0.10 to 0.28. Catalytic ignition is inhibited by rising pressure and increasing hydrogen concentration. However, at temperatures above the catalytic ignition temperature T_ign, the dependencies of the heterogeneous reactivity reverse, showing a positive order ～1.5 with respect to hydrogen concentration and an overall positive pressure order of ～0.97. Despite the longer catalytic ignition times for the larger equivalence ratios, the times required to reach steady state are shorter at larger stoichiometries due to their enhanced catalytic reactivity at T > T_ign and the resulting higher exothermicity. Following catalytic ignition, the wall temperatures eventually attain superadiabatic values due to the diffusional imbalance of hydrogen. Homogeneous chemistry considerably moderates the superadiabatic surface temperatures at 5 bar, as the gaseous combustion zone extends parallel to the channel wall and thus shields the catalyst surface from the hydrogen-rich channel core. Furthermore, gas-phase chemistry reduces the steady-state times and substantially increases the hydrogen conversion.     

Laser induced fluorescence of formaldehyde and Raman measurements of major species during partial catalytic oxidation of methane with large H2O and CO2 dilution at pressures up to 10 bar

The catalytic partial oxidation (CPO) of CH₄/O₂ mixtures diluted with large amounts of H₂O and CO₂ (up to 43% and 21% vol., respectively) was investigated experimentally and numerically in the pressure range 4 bar  p  10 bar. Experiments were carried out in an optically accessible channel-flow catalytic reactor coated with Rh/ZrO₂, and included planar laser induced fluorescence (LIF) of formaldehyde for the assessment of homogeneous (gas-phase) ignition and one-dimensional spontaneous Raman measurements of all major gas-phase species for the evaluation of the heterogeneous (catalytic) processes. Simulations were performed with a full elliptic model that included detailed heterogeneous and homogeneous chemical reaction schemes. Over the reactor length with negligible gas-phase chemistry contribution, the employed heterogeneous reaction scheme provided good agreement to the measured methane consumption and synthesis gas yields, overpredicting mildly the partial over the total oxidation route. It was shown that the added water provided a source of O(s) and OH(s) surface radicals that enhanced the methane conversion and H₂ yields and reduced the CO yields. Moreover, the addition of CO₂ had a negligible chemical effect on the aforementioned parameters. An increase in pressure from 4 to 10 bar had a minor impact on the methane conversion and hydrogen selectivity. The employed gaseous scheme reproduced the LIF-measured onset of homogeneous ignition, although it underpredicted the extent of the formaldehyde zone ahead of the flame and the flame propagation characteristics at the highest investigated pressure (10 bar).     

Homogeneous ignition of CH4/air and H2O and CO2-diluted CH4/O2 mixtures over Pt; an experimental and numerical investigation at pressures up to 16 bar

The homogeneous ignition of CH₄/air, CH₄/O₂/H₂O/N₂, and CH₄/O₂/CO₂/N₂ mixtures over platinum was investigated experimentally and numerically at pressures 4 bar p 16 bar, temperatures 1120 K T 1420 K, and fuel-to-oxygen equivalence ratios 0.30 0.40. Experiments have been performed in an optically accessible catalytic channel-flow reactor and included planar laser induced fluorescence (LIF) of the OH radical for the determination of homogeneous (gas-phase) ignition and one-dimensional Raman measurements of major species concentrations across the reactor boundary layer for the assessment of the heterogeneous (catalytic) processes preceding homogeneous ignition. Numerical predictions were carried out with a 2D elliptic CFD code that included elementary heterogeneous and homogeneous chemical reaction schemes and detailed transport. The employed heterogeneous reaction scheme accurately captured the catalytic methane conversion upstream of the gaseous combustion zone. Two well-known gas-phase reaction mechanisms were tested for their capacity to reproduce measured homogeneous ignition characteristics. There were substantial differences in the performance of the two schemes, which were ascribed to their ability to correctly capture the p–T– parameter range of the self-inhibited ignition behavior of methane. Comparisons between measured and predicted homogeneous ignition distances have led to the validation of a gaseous reaction scheme at 6 bar p 16 bar, a pressure range of particular interest to gas-turbine catalytically stabilized combustion (CST) applications. The presence of heterogeneously produced water chemically promoted the onset of homogeneous ignition. Experiments and predictions with CH₄/O₂/H₂O/N₂ mixtures containing 57% per volume H₂O have shown that the validated gaseous scheme was able to capture the chemical impact of water in the induction zone. Experiments with CO₂ addition (30% per volume) were in good agreement with the numerical simulations and have indicated that CO₂ had only a minor chemical impact on homogeneous ignition.