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

EFFET DE LA SALINITE SUR LA RETENTION EN EAU DES SOLS GYPSEUX DE LA REGION DE AIN BENOUI (BISKRA) Effect of salinity on the retention of water by gypseous soils in Ain Benoui region (Biskra)

Les sols étudiés sont situés dans la séquence allant de Djebel Bougzel dans la partie amont jusqu'à la Sebkha dans la partie avale, dans la région de Ain Benoui, commune d’El Hadjeb, dans le sud – ouest de Biskra. Cette région se caractérise par un climat aride, avec la présence d’une nappe phréatique qui est généralement salée et un matériau gypso-calcaire. Les résultats de cette étude montrent une diminution de l’humidité avec l’augmentation de la succion dans toutes les classes étudiées. En outre, l’humidité tend à s’élever avec l’élévation de la salinité et cela en partant de la première classe (CE : 1.87 dS/m) jusqu'à la dernière (CE : 134 dS/m), avec un accroissement dans les sols à texture fine. The studied soils are located in the sequence going of Djebel Bougzel in the upstream part until Sebkha in the downstream part, in the area of Ain Benoui, commune of El Hadjeb, in the south-west of Biskra. This region is characterized by an arid climate, with the presence of a ground water which is generally salted and a material gypso-calcareous. The results of this study show a reduction in moisture with the increase in suction in all the studied classes. Moreover, moisture tends to rise with the rise in salinity and that on the basis of first class (EC: 1.87 dS/m) until last (EC: 134 dS/m), with an increase in soils with fine texture

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

Contribution of ETM+ images and GIS for detecting dynamic changes in the steppe area of Naâma, Algeria

Ce travail met en évidence l’apport des images Landsat pour le suivi dynamique de l’espace steppique dans une aride  (Algérie). L’analyse qualitative et quantitative de l’évolution rapide du paysage et plus particulièrement l’évolution de l’ensablement dans les communes s’avère intéressante dans la mesure où elle permet de dresser un bilan provisoire sur l’état actuel de la zone d’étude. Pour l’analyse, les changements de l’état de surface intervenus entre 1957 et 2002 extraient à partir des images MSS, TM et ETM+ de Landsat ont été retenus. Dès lors, trois méthodes de détections des changements (identification rapide et quantification de l’évolution des changements, technique de la composition colorée diachronique et la méthode indice dynamique de couverture des sols) ont été utilisées afin de localiser les différentes zones qui ont subi des mutations profondes et plus particulièrement l’extension de l’ensablement et la dégradation des sols à l’intérieur des contrées de la wilaya de Naâma. Il est important de noter que nous nous sommes basés sur  le modèle d’Olsson (1994)  pour les corrections atmosphériques des images. La zone concernée par cette étude fait partie des hautes plaines oranaises. Elle se rattache administrativement à la wilaya de Naâma. Elle s’étend sur une superficie de 29 825 km2, entre 32°08’ et 34°16’ de latitude nord et 0°09’ et 1°43’ de longitude ouest. L’utilisation des données de télédétection au travers de l’indice dynamique de couverture des sols et de la composition colorée diachronique a permis de mettre en évidence les différents changements qui ont eu lieu de 1987 à 2002. Ces changements concernant les mutations des unités paysagères en zone steppique ont nécessité de tester plusieurs indices de changement (indice de végétation, indice de brillance, indice de curasse et l’analyse en composante en principale) afin de minimiser les erreurs sur l’appréciation des résultats sur les changements. En effet, ces différents traitements ont révélé que pour l’ensemble de la région d’étude, la surface des espaces ensablés est passée de 1,38 % en 1957 à 42,9 % en 2002, soit une superficie de 1 280 762 ha; ce qui correspond à une extension de 28 461,4 ha par an.  Mots clés: Dégradation, Détection de changement, Ensablement, Télédétection, Naâma, AlgérieIn this work we propose to highlight the Landsat images contribution for the dynamic monitoring of steppe area. We retained for our analysis, the changes  in the soil surface state occurred since 1957 up to 2002 from MSS, TM and ETM+ images of Landsat. From that time on, three methods of detection of changes were used so as to locate the various areas, which are affected, by a major changes and the sanding up extension inside the studied area of the department of Naâma. These images of Landsat showed an alarming of the sand extension.  Indeed, this analysis revealed that for the all the studied area, the sanding up of space surface passed from 1.38 % in 1957 to 42.9 % in 2002, that is a surface of 1 280 762 ha; what corresponds to an extension of 28 461.4 ha per year. Keywords:  change detection, sanding Up, remote sensing, Naâm

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

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

Solid-state ion exchange of Fe in small pore SSZ-13 zeolite: Characterization of the exchanged species and their relevance for the NOx SCR reaction

Solid state ion exchange was performed for the successful introduction of Fe cations in the small pore CHA structured SSZ-13 zeolite. The produced catalysts were characterized by IR and UV-Vis spectroscopies and thermally programmed reaction techniques to probe the Fe sites formed during the exchange and the catalytic activity for the NOx SCR reaction. The results indicate that highly dispersed and heterogeneous Fe sites are formed, and the type depends on the Al distribution in the zeolite. Dimeric Fe species are formed preferentially at the start of the exchange on the 6- and 8-member rings that contain at least two Al exchange sites and once these sites are fully saturated the Fe is exchanged as isolated cations