Experimental and Numerical Study of Low Temperature Methane Steam Reforming for Hydrogen Production

Low temperature methane steam reforming for hydrogen production, using experimental developed Ni/Al2O3 catalysts is studied both experimentally and numerically. The catalytic activity measurements were performed at a temperature range of 500–700 °C with steam to carbon ratio (S/C) of 2 and 3 under atmospheric pressure conditions. A mathematical analysis to evaluate the reaction feasibility at all different conditions that have been applied by using chemical equilibrium with applications (CEA) software and in addition, a mathematical model focused on the kinetics and the thermodynamics of the reforming reaction is introduced and applied using a commercial finite element analysis software (COMSOL Multiphysics 5.0). The experimental results were employed to validate the extracted simulation data based on the yields of the produced H2, CO2 and CO at different temperatures. A maximum hydrogen yield of 2.7 mol/mol-CH4 is achieved at 700 °C and S/C of 2 and 3. The stability of the 10%Ni/Al2O3 catalyst shows that the catalyst is prone to deactivation as supported by Thermogravimetric Analysis TGA results

The application of inelastic neutron scattering to investigate the ‘dry’ reforming of methane over an alumina-supported nickel catalyst operating under conditions where filamentous carbon formation is prevalent

The use of CO2 in reforming methane to produce the industrial feedstock syngas is an economically and environmentally attractive reaction. An alumina-supported nickel catalyst active for this reaction additionally forms filamentous carbon. The catalyst is investigated by inelastic neutron scattering as well as elemental analysis, temperature-programmed oxidation, temperature-programmed hydrogenation, X-ray diffraction, transmission electron microscopy and Raman scattering. Isotopic substitution experiments, using 13CO2 for 12CO2, show the oxidant to contribute to the carbon retention evident with this sample. At steady-state operation, a carbon mass balance of 95 % is observed. A kinetic scheme is proposed to account for the trends observed

Statistical models of diffusion and aggregation for coke formation in a catalyst pore

We simulated models of diffusion and aggregation in long pores of small widths in order to represent the basic mechanisms of coke deposition in catalysts' pores. Coke precursors are represented by particles injected at the pore entrance. Knudsen diffusion, which is usually expected inside the pores, is modeled by ballistic motion of those particles. The regime of molecular diffusion is also analyzed via models of lattice random walks biased along the pores. The aggregation at the surface or near previously aggregated particles was modeled by different probabilistic rules, accounting for the possibilities of more compact or more ramified deposits. In the model of Knudsen diffusion and in some cases of molecular diffusion, there is an initial regime of uniform deposition along the pore, after which the deposits acquire an approximately wedge shape, with the pore plugging near its entrance. After the regime of uniform deposition and before that of critical pore plugging, the average aggregation position slowly decreases with the number N of deposited particles approximately as N^{-0.25}. The apparently universal features of deposits generated by microscopic models are compared with those currently adopted in continuum models.Comment: 14 pages (figures included), to appear in Physica

Ethane steam reforming over a platinum/alumina catalyst: effect of sulphur poisoning

In this study we have examined the adsorption of hydrogen sulfide and methanethiol over platinum catalysts and examined the effect of these poisons on the steam reforming of ethane. Adsorption of hydrogen sulfide was measured at 293 and 873 K. At 873 K the adsorbed state of hydrogen sulfide in the presence of hydrogen was SH rather than S, even though the Pt:S ratio was unity. The effect of 11.2 ppm hydrogen sulfide or methanethiol on the steam reforming of ethane was studied at 873 K and 20 barg. Both poisons deactivated the catalyst over a number of hours, but methanethiol was found to be more deleterious, reducing the conversion by almost an order of magnitude, possibly due to the co-deposition of sulfur and carbon. Changes in the selectivity revealed that the effect of sulfur was not uniform on the reactions occurring, with the production of methane reduced proportionally more than the other products, due to the surface sensitivity of the hydrogenolysis and methanation reactions. The water-gas shift reaction was affected to a lesser extent. No regeneration was observed when hydrogen sulfide was removed from the feedstream in agreement with adsorption studies. A slight regeneration was observed when methanethiol was removed from the feed, but this was believed to be due to the removal of carbon rather than sulfur. The overall effect of sulfur poisoning was to reduce activity and enhance hydrogen selectivity

Kohlenstoffbildung auf Nickel und Nickel-Kupfer-Legierungskatalysatoren

Equilibrium, kinetic and morphological studies of carbon formation in CH4+H2, CO, and CO+H2 gases on silica supported nickel and nickel-copper catalysts are reviewed. The equilibrium deviates in all cases from graphite equilibrium and more so in CO+CO2 than in CH4+H2. A kinetic model based on information from surface science results with chemisorption of CH4 and possibly also the first dehydrogenation step as rate controlling describes carbon formation on nickel catalyst in CH4+H2 well. The kinetics of carbon formation in CO and CO+H2 gases are in agreement with CO disproportionation as rate determining step. The presence of hydrogen influences strongly the chemisorption of CO. Carbon filaments are formed when hydrogen is present in the gas while encapsulating carbon dominates in pure CO. Small amounts of Cu alloying promotes while larger amounts (Cu : Ni ≥ 0.1) inhibits carbon formation and changes the morphology of the filaments ("octopus" carbon formation). Adsorption induced nickel segregation changes the kinetics of the alloy catalysts at high carbon activities. Modifications suggested in some very recent papers on the basis of new results are also briefly discussed.Center for Surface Reactivity

The impact of schizophrenia and intelligence on the relationship between age and brain volume

Age has been shown to have an impact on both grey (GM) and white matter (WM) volume, with a steeper slope of age-related decline in schizophrenia compared to healthy controls. In schizophrenia, the relation between age and brain volume is further complicated by factors such as lower intelligence, antipsychotic medication, and cannabis use, all of which have been shown to have independent effects on brain volume. In a study of first-episode, antipsychotic-naïve schizophrenia patients (N = 54) and healthy controls (N = 56), we examined the effects of age on whole brain measures of GM and WM volume, and whether these relationships were moderated by schizophrenia and intelligence (IQ). Secondarily, we examined lifetime cannabis use as a moderator of the relationship between age and brain volume. Schizophrenia patients had lower GM volumes than healthy controls but did not differ on WM volume. We found an age effect on GM indicating that increasing age was associated with lower GM volumes, which did not differ between groups. IQ did not have a direct effect on GM, but showed a trend-level interaction with age, suggesting a greater impact of age with lower IQ. There were no age effects on WM volume, but a direct effect of IQ, with higher IQ showing an association with larger WM volume. Lifetime cannabis use did not alter these findings significantly. This study points to effects of schizophrenia on GM early in the illness, before antipsychotic treatment is initiated, suggesting that WM changes may occur later in the disease process