Insights on a methanation catalyst aging process: Aging characterization and kinetic study

Power to gas systems is one of the most interesting long-term energy storage solutions. As a result of the high exothermicity of the CO2 methanation reaction, the catalyst in the methanation subsystem is subjected to thermal stress. Therefore, the performance of a commercial Ni/Al2O3 catalyst was investigated over a series of 100 hour-long tests and in-process relevant conditions, i.e. 5 bar from 270 to 500 °C. Different characterization techniques were employed to determine the mechanism of the observed performance loss (N2 physisorption, XRD, TPO). The TPO analysis excluded carbon deposition as a possible cause of catalyst aging. The BET analysis evidenced a severe reduction in the total surface area for the catalyst samples tested at higher temperatures. Furthermore, a direct correlation was found between the catalyst activity decline and the drop of the catalyst specific surface. In order to correctly design a reliable methanation reactor, it is essential to have a kinetic model that includes also the aging kinetics. For this purpose, the second set of experiments was carried out, in order to determine the intrinsic kinetics of the catalyst. The kinetic parameters were identified by using nonlinear regression analysis. Finally, a power-law aging model was proposed to consider the performance loss in time

Experimental and numerical investigations of a river embankment model under transient seepage conditions

The evaluation of riverbank stability often represents an underrated problem in engineering practice, but is also a topical geotechnical research issue. In fact, it is certainly true that soil water content and pore water pressure distributions in the riverbank materials vary with time, due to the changeable effects of hydrometric and climatic boundary conditions, strongly influencing the bank stability conditions. Nonetheless, the assessment of hydraulic and mechanical behavior of embankments are currently performed under the simplified hypothesis of steady\u2010state seepage, generally neglecting the unsaturated soil related issues. In this paper, a comprehensive procedure for properly defining the key aspects of the problem is presented and, in particular, the soil characterization in partially saturated conditions of a suitably compacted mixture of sand and finer material, typical of flood embankments of the main river Po tributaries (Italy), is reported. The laboratory results have then been considered for modelling the embankment performance under transient seepage and following a set of possible hydrometric peaks. The outcome of the present contribution may provide meaningful geotechnical insights, for practitioners and researchers, in the flood risk assessment of river embankments

Life cycle assessment of the biofuel production from lignocellulosic biomass in a hydrothermal liquefaction - aqueous phase reforming integrated biorefinery

The use of biofuels in the transport sector is one of the strategies for its decarbonization. Here, the LCA meth-odology was used for the first time to assess the environmental impacts of a biorefinery where hydrothermal liquefaction (HTL) and aqueous phase reforming (APR) were integrated. This novel coupling was proposed to valorize the carbon loss in the HTL-derived aqueous phase, while simultaneously reducing the external H2 de-mand during biocrude upgrading. Corn stover (residue) and lignin-rich stream (waste) were evaluated as possible lignocellulosic feedstocks. The global warming potential (GWP) was 56.1 and 58.4 g CO2 eq/MJbiofuel, respec-tively. Most of the GWP was attributable to the electrolysis step in the lignin-rich stream case and to the thermal duty and platinum use in the corn stover case. Other impact categories were investigated, and an uncertainty analysis was also carried out. A sensitivity analysis on biogenic carbon, electricity/thermal energy source and alternative hydrogen supply was conducted to estimate their influence on the GWP. Finally, the two scenarios were compared with the environmental impact of fossil-and other biomass-derived fuels, also considering fuel utilization. HTL-APR allowed a 37% reduction compared to fossil diesel, further reduced to 80% with the lignin -rich stream when green energy was used

Folding mechanisms steer the amyloid fibril formation propensity of highly homologous proteins

Significant advances in the understanding of the molecular determinants of fibrillogenesis can be expected from comparative studies of the aggregation propensities of proteins with highly homologous structures but different folding pathways. Here, we fully characterize, by means of stopped-flow, T-jump, CD and DSC experiments, the unfolding mechanisms of three highly homologous proteins, zinc binding Ros87 and Ml153-149 and zinc-lacking Ml452-151. The results indicate that the three proteins significantly differ in terms of stability and (un)folding mechanisms. Particularly, Ros87 and Ml153-149 appear to be much more stable to guanidine denaturation and are characterized by folding mechanisms including the presence of an intermediate. On the other hand, metal lacking Ml452-151 folds according to a classic two-state model. Successively, we have monitored the capabilities of Ros87, Ml452-151 and Ml153-149 to form amyloid fibrils under native conditions. Particularly, we show, by CD, fluorescence, DLS, TEM and SEM experiments, that after 168 hours, amyloid formation of Ros87 has started, while Ml153-149 has formed only amorphous aggregates and Ml452-151 is still monomeric in solution. This study shows how metal binding can influence protein folding pathways and thereby control conformational accessibility to aggregation-prone states, which in turn changes aggregation kinetics, shedding light on the role of metal ions in the development of protein deposition diseases

Aqueous phase reforming of pilot-scale Fischer-Tropsch water effluent for sustainable hydrogen production

Fischer-Tropsch (FT) synthesis produces an aqueous stream containing light oxygenates as major by-product. The low carbon concentration of the organics makes its thermal recovery unprofitable. Thus, novel processes are needed to utilize this waste carbon content. In this work, the aqueous phase reforming of the wastewater obtained from a 15 kWth Fischer-Tropsch plant was explored as a promising process to produce hydrogen at mild temperatures. The FT product water was firstly characterized and afterward subjected to the reforming at different reaction temperatures and time, using a platinum catalyst supported on activated carbon. It was observed that, besides activity, the selectivity towards hydrogen was favored at higher temperatures; equally, increasing the reaction time allowed to obtain the total conversion of most molecules found in the solution, without decreasing the selectivity and reaching a plateau at 4 hours in the hydrogen productivity. In order to get more insights into the reaction mechanism and product distribution derived from the APR of FT product water, several tests were performed with single compounds, finding characteristic features. The importance of the position of the hydroxyl group in the molecule structure was highlighted, with secondary alcohols more prone to dehydrogenation pathways compared to primary alcohols. Moreover, no interference among the substrates was reported despite the mixture is constituted by several molecules: in fact, the results obtained with the real FT product water were analogous to the linear combination of the single compound tests. Finally, the reuse of the catalyst showed no appreciable deactivation phenomena

Aqueous phase reforming of the residual waters derived from lignin-rich hydrothermal liquefaction: investigation of representative organic compounds and actual biorefinery streams

Secondary streams in biorefineries need to be valorized to improve the economic and environmental sustainability of the plants. Representative model compounds of the water fraction from the hydrothermal liquefaction (HTL) of biomass were subjected to aqueous phase reforming (APR) to produce hydrogen. Carboxylic and bicarboxylic acids, hydroxyacids, alcohols, cycloketones and aromatics were identified as model compounds and tested for APR. The tests were performed with a Pt/C catalyst and the influence of the carbon concentration (0.3–1.8 wt. C%) was investigated. Typically, the increase of the concentration negatively affected the conversion of the feed toward gaseous products, without influencing the selectivity toward hydrogen production. A synthetic ternary mixture (glycolic acid, acetic acid, lactic acid) was subjected to APR to evaluate any differences in performance compared to the tests with single compounds. Indeed, glycolic acid reacted faster in the mixture than in the corresponding single compound test, while acetic acid remained almost unconverted. The influence of the reaction time, temperature and carbon concentration was also evaluated. Finally, residual water resulting from the HTL of a lignin-rich stream originating from an industrial-scale lignocellulosic ethanol process was tested for the first time, after a thorough characterization. In this framework, the stability of the catalyst was studied and found to be correlated to the presence of aromatics in the aqueous feedstock. For this reason, the influence of an extraction procedure for the selective removal of these compounds was explored, leading to an improvement in the APR performance

A multidisciplinary study on the spatial variability of the local stratigraphic conditions in partially saturated slopes for flow-like landslide prediction

Flow-like landslides, which occur mainly in shallow granular deposits resting on steep bedrock, represent a major natural hazard worldwide. The pore water pressure distribution and the soil water content directly affect the soil shear strength, thus controlling the triggering of these landslides. Criticalgeomorphological and topographical settings, together with peculiar stratigraphic and hydrogeological features, are commonly recognized as predisposing factors for flow-like landslides occurrence. Hence, investigating the spatial and temporal variability of hydraulic slope conditions is a fundamental activity that consists of identifying local geological factors and seasonal monitoring of the subsurface water regime. The present work proposes an integrated geological, geophysical and geotechnical approach to identify the spatial variability of the local stratigraphic setting and hydrogeological conditions in a partially saturated slope, in order to set up a procedure able to provide a prediction of the flow-like landslides occurrence atslope scale. The multidisciplinary study has been applied to a test site on Mt. Faito, in the Lattari Mts. (Southern Italy), where extensive geophysical, geological and geotechnical soil characterization and in situmonitoring data collected over two years are available

SO2 deactivation mechanism of NO oxidation and regeneration of the LaCoO3 perovskite

The deactivation mechanism and methods to cope with the poisoning by SO2 of LaCoO3 perovskite-based NO oxidation catalysts were investigated. The LaCoO3 perovskite was synthesized by a sol-gel method and the fresh, sulphate-deactivated and regenerated catalysts were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, H2-and soot-temperature programmed reduction, temperature programmed desorption and diffuse reflectance infrared Fourier transform spectroscopy. The SO2 poisoning strongly affected the NO oxidation activity. It was demonstrated that the deactivation mechanism proceeds in two stages: initially the active sites with a basic character are blocked by SO3 and subsequently the lanthanum sulphate salts grow progressively on the surface and cobalt is unaffected. Above 500 °C, the surface bound sulphates become mobile and migrate into the bulk of the catalyst. Several prevention and regeneration methods were proposed and tested. By mixing the catalyst with Ca(OH)2 as an adsorbent nearly 50% of the original activity was retained. Regeneration by diesel soot was presented here for the first time, where the blocking oxygen can spill over to the soot oxidizing it and releasing the bound sulphur as SO2 and CO2. Furthermore, a facile regeneration method was explored by washing the deactivated catalyst to dissolve the small amounts of sulphates on the surface