Search

Abstract: The CO2 capture properties of a new nanocrystalline CaO-based mixed oxide (CaCeZrO x ) were studied in both TGA and a fixed bed reactor. The kinetics of CO2 capture at dry conditions was compared between these two reactors. The application of the new CO2 acceptor in sorption enhanced steam methane reforming was studied by a fixed-bed reactor in the presence of 40wt% nickel hydrotalcite catalysts. Experimental results show that the new CO2 acceptor, CaCeZrO x has a significantly improved CO2 capture capacity and cyclic reaction stability compared to natural dolomites, because of the large pores and stable backbone structure. It has also been observed that the sorption enhanced steam methane reforming in the fixed bed reactor produces more than 95% H2 in a single-step process. Increase in production of hydrogen and higher CO2 capture capacity are also observed with an increase in the residence time of methane. Steam has a significant effect on the stability of the acceptors, but not very much on the kinetics and capacity of CO2 capture. The capacity of CO2 capture on the acceptors in the SESMR process cannot be predicted by the independent CO2 capture kinetic study on acceptor alone. A synergy effect between the sorption enhanced reactions and CO2 capture on the CO2 capture capacity was observed on the all solid CaO based CO2 acceptors. [Copyright &y& Elsevier]

Aqueous phase reforming (APR) of ethylene glycol was performed at 225 °C and 30 bar in batch and continuous reaction conditions. The effect on the APR performance by functionalizing carbon supports with nitrogen and adding Mn to Pt-based catalysts was investigated. The presence of nitrogen species on the carbon surface and Mn-addition (PtMn) improved the catalytic activity and promoted H 2 production. XPS results suggest that the enhancement of the catalytic activity may be attributed to charge transfer from platinum to the nitrogen groups and Mn. Pt-based catalysts were stable under the studied reaction conditions, while up to 97 % of the manganese leached into the liquid solution during APR. However, the catalytic activity was maintained even with such significant decrease in Mn content, indicating that only a small amount of Mn is necessary to maintain the promotional effect on Pt during APR. [Display omitted] • Electronic interactions between Pt-N and Pt-Mn led to enhanced catalytic activity. • N-doped carbon nanofibers effectively improved H 2 yield in aqueous phase reforming. • Pt-based catalyst promoted with Mn presented higher H 2 yield and selectivity. • Metal-support interactions are key factors in promoting catalytic activity. [ABSTRACT FROM AUTHOR]

• Small Ni particles exhibit higher steam methane reforming activity than large ones. • The size-dependent activity of Ni catalysts is related to the surface-dependent activity. • Ni(2 1 1) is the most active surface for steam methane reforming. • Decreased Ni(2 1 1) surface fraction results in reduced Ni activity as size increases. Fundamental understanding of the size-dependent activity is essential to harness powers of the nanocatalysts. Here we report an experimental and theoretical study of the Ni particle size effect on activity of steam methane reforming (SMR) to achieve a better understanding of the size dependence of kinetic behavior at an atomic level. A kinetic study illustrated the higher forward methane turnover frequency on the smaller sized Ni particles. The size-dependent activity was well reproduced by microkinetic modeling on a truncated octahedron model with the kinetic parameters estimated by the improved unity bond index-quadratic exponential potential (UBI-QEP) and the Brønsted–Evans–Polanyi (BEP) relationship. Microkinetic modeling suggested that the size-dependent activity of Ni catalysts is associated with the surface-dependent activity. Much higher activity of Ni(2 1 1) than Ni(1 1 1) and Ni(1 0 0) accompanied by decreased Ni(2 1 1) surface fraction results in reduced Ni activity as particle size increases. The activity of Ni(1 1 1) is limited by high free energy barriers, while that of Ni(1 0 0) is limited by site blockage by C* and CH*. This work offers a feasible approach to gain insight into size-dependent activity and to aid rational catalyst design for SMR in which preparing extremely small Ni particles (≤6 nm) might be a good strategy. [ABSTRACT FROM AUTHOR]

High-purity H 2 was produced by the sorption enhanced steam reforming (SESR) of acetic acid, a model compound of bio-oil obtained from the fast pyrolysis of biomass, in a fluidized bed reactor. A Pd/Ni–Co hydrotalcite-like material (HT) and dolomite were used as reforming catalyst and CO 2 sorbent, respectively. The hydrogen yield and purity were optimized by response surface methodology (RSM) and the combined effect of the reaction temperature ( T ), steam-to-carbon molar ratio in the feed (steam/C) and weight hourly space velocity (WHSV) upon the sorption enhanced steam reforming process was analyzed. T was studied between 475 and 675 °C, steam/C ratio between 1.5 and a 4.5 mol/mol and WHSV between 0.893 and 2.679 h −1 . H 2 yield, H 2 selectivity and H 2 purity, as well as the CH 4 , CO and CO 2 concentrations in the effluent gas, were assessed. The operating temperature proved to be the variable that had the greatest effect on the response variables studied, followed by the WHSV and the steam/C ratio. The results show that the H 2 yield, H 2 selectivity and H 2 purity increased, while the CH 4 , CO and CO 2 concentrations decreased, concurrently with the temperature up to around 575–625 °C. Higher values of the steam/C ratio and lower WHSV values favored the H 2 yield, H 2 selectivity and H 2 purity, and reduced the CH 4 concentration. It was found that the SESR of acetic acid at atmospheric pressure and 560 °C, with a steam/C ratio of 4.50 and a WHSV of 0.893 h –1 gave the highest H 2 yield of 92.00%, with H 2 purity of 99.53% and H 2 selectivity of 99.92%, while the CH 4 , CO and CO 2 concentrations remained low throughout (0.04%, 0.06% and 0.4%, respectively). The results also suggested that a slow CO 2 capture rate led to a poor level of hydrogen production when the SESR process was carried out at low temperatures, although this can be improved by increasing the sorbent/catalyst ratio in the fluidized bed. [ABSTRACT FROM AUTHOR]

Abstract: First-principles calculations have been performed to examine the effect of doped Ag on the kinetics of Ni-catalyzed methane dissociation and coke formation. The close-packed Ag/Ni(111) and stepped Ag/Ni(211) surfaces as well as the defect facets with step sites blocked by Ag or C atoms are constructed to investigate the role of the coordinatively unsaturated sites in the catalytic performance of Ni nanoparticles. The most stable CH x (x =0–4) adsorption configurations and transition states for methane dissociation have been identified on both Ni and Ag/Ni surfaces. The calculated results indicate that the activation energy for methane dissociation is increased with the Ag coverage on Ni(111), and the C atoms deposited on the catalyst surface can be readily separated into small islands by Ag. On Ni(211) Ag atoms are predicted to bind preferentially to the middle-step sites which act as the nucleation center for the growth of filamentous carbon and therefore have the potential to prevent catalyst particles from being destroyed. Meanwhile, as the energy barrier for methane dissociation on the Ag-blocked Ni(211) surface is even higher than that on pure Ni(111), the active center is transferred from the stepped surface to the close-packed surface. These findings provide a rational interpretation of the experimental observations that Ag/Ni catalyst exhibits lower catalytic activity towards steam methane reforming but high resistance to coke deposition. [Copyright &y& Elsevier]