Catalytic performance of Ni supported apatite-type lanthanum silicates Ni/ATLS-(Ni/La9.83Si4.5Fe1.5O26±δ) in glycerol steam reforming reaction

The disposal of crude glycerol as a by-product of the biodiesel industry is one of the major issues concerning its utilization towards the production for renewable oxygen. Among the various methods of such utilization, the Glycerol Steam Reforming (GSR) reaction has been investigated over various metal supported catalysts with Ru, Rh, Pt, Ni, Co and Fe to be active. In addition, Ni appears as the most promising active metal, due to its low cost, its ability towards O–H, C–H and C–C dissociation even more effectively than noble metals. On the other hand, apatite type lanthanum silicate (ATLS) materials, as solid oxide electrolytes, have interesting redox properties, high oxygen mobility mainly through interstitial oxygen mobility. However only scarce data is yet available on their catalytic properties although promising. In this work we report for the first time an ATLS as Ni support in the GSR reaction with promising performance in comparison with alumina supports

Investigating the correlation between deactivation and the carbon deposited on the surface of Ni/Al2O3 and Ni/La2O3-Al2O3 catalysts during the biogas reforming reaction

Ni/Al2O3 and Ni/La2O-Al2O3 catalysts were investigated for the biogas reforming reaction using CH4/CO2 mixtures with minimal dilution. Stability tests at various reaction temperatures were conducted and TGA/DTG, Raman, STEM-HAADF, HR-TEM, XPS techniques were used to characterize the spent samples. Graphitized carbon allotrope structures, carbon nanotubes (CNTs) and amorphous carbon were formed on all samples. Metallic Ni0 was recorded for all (XPS), whereas a strong peak corresponding to Ni2O3/NiAl2O4, was observed for the Ni/Al sample (650–750 °C). Stability tests confirm that the Ni/LaAl catalyst deactivates at a more gradual rate and is more active and selective in comparison to the Ni/Al for all temperatures. The Ni/LaAl exhibits good durability in terms of conversion and selectivity, whereas the Ni/Al gradually loses its activity in CH4 and CO2 conversion, with a concomitant decrease of the H2 and CO yield. It can be concluded that doping Al2O3 with La2O3 stabilizes the catalyst by (a) maintaining the Ni0 phase during the reaction, due to higher dispersion and stronger active phase-support interactions, (b) leading to a less graphitic and more defective type of deposited carbon and (c) facilitating the deposited carbon gasification due to the enhanced CO2 adsorption on its increased surface basic sites

The effect of noble metal (M: Ir, Pt, Pd) on M/Ce2 O3-¿-Al2 O3 catalysts for hydrogen production via the steam reforming of glycerol

A promising route for the energetic valorisation of the main by-product of the biodiesel industry is the steam reforming of glycerol, as it can theoretically produce seven moles of H2 for every mole of C3 H8 O3. In the work presented herein, CeO2 –Al2 O3 was used as supporting material for Ir, Pd and Pt catalysts, which were prepared using the incipient wetness impregnation technique and characterized by employing N2 adsorption–desorption, X-Ray Diffraction (XRD), Temperature Programmed Reduction (TPR), Temperature Programmed Desorption (TPD), X-ray Photoelectron Spectroscopy (XPS) and Transmission Electron Microscopy (TEM). The catalytic experiments aimed at identifying the effect of temperature on the total conversion of glycerol, on the conversion of glycerol to gaseous products, the selectivity towards the gaseous products (H2, CO2, CO, CH4) and the determination of the H2 /CO and CO/CO2 molar ratios. The main liquid effluents produced during the reaction were quantified. The results revealed that the Pt/CeAl catalyst was more selective towards H2, which can be related to its increased number of Brønsted acid sites, which improved the hydrogenolysis and dehydrogenation–dehydration of condensable intermediates. The time-on-stream experiments, undertaken at low Water Glycerol Feed Ratios (WGFR), showed gradual deactivation for all catalysts. This is likely due to the dehydration reaction, which leads to the formation of unsaturated hydrocarbon species and eventually to carbon deposition. The weak metal–support interaction shown for the Ir/CeAl catalyst also led to pronounced sintering of the metallic particles

Energy and Exergy-Based Screening of Various Refrigerants, Hydrocarbons and Siloxanes for the Optimization of Biomass Boiler–Organic Rankine Cycle (BB–ORC) Heat and Power Cogeneration Plants

The cogeneration of power and heat was investigated for Biomass Boiler–Organic Rankine Cycle (BB–ORC) plants with the characteristics of typical units, such as the 1 MWel Turboden ORC 10 CHP. The thermodynamic analysis of the ORC unit was undertaken considering forty-two (42) dry and isentropic candidate pure working fluids. Only subcritical Rankine cycles were considered, and the pinch point temperature differences for the evaporation and condensation heat exchangers were kept constant at 10 °C in all cases. The study provides an original and unique screening of almost all pure working fluids that are considered appropriate in the literature under the same operation and optimization conditions and compiles them into a single reference. In its conclusions, the study provides useful fluid selection and design guidelines, which may be easily followed depending on the optimization objective of the ORC designer or operator. In general, hydrocarbons are found to lie in the optimum middle range of the fluid spectrum, between the siloxanes that maximize the production of mechanical power and the refrigerants that maximize the production of heat. Specific hydrocarbon fluids, such as cyclopentane, heptane, hexane, benzene, and toluene, are found as rational options for maximum mechanical efficiency when operating with practically feasible condensation pressures between 10 and 200 kPa. At condensation pressures below 10 kPa, ethylbenzene, o-xylene, m-xylene, p-xylene, and nonane are also found to be feasible options. Finally, cyclopentane, hexane, and MM (hexamethyldisiloxane) are selected as the most appropriate options for cogeneration plants aiming simultaneously at high mechanical power and maximum temperature water production. © 2022 by the authors

Halloysite nanotubes noncovalently functionalised with SDS anionic surfactant and PS-b-P4VP block copolymer for their effective dispersion in polystyrene as UV-blocking nanocomposite films

Asimple and versatilemethod is reported for the noncovalent functionalisation of natural and "green" halloysite nanotubes (HNTs) allowing their effective dispersion in a polystyrene (PS) thermoplastic matrix via solvent mixing. Initially, HNTs (pristine HNTs) were modified with physically adsorbed surfactant molecules of sodium dodecyl sulphate (SDS) and PS-b-P4VP [P4VP: poly(4-vinylpyridine)] block copolymer (BCP). Hereafter, SDS and BCP modified HNTs will be indicated as SDS-m-HNT and BCP-m-HNT.Nanocomposite films with 1, 2, and 5 wt.%HNTloadingswere prepared, abbreviated as PS-SDS-m-HNT1, PS-SDS-m-HNT2, and PS-SDS-m-HNT5 and PS-BCP-m-HNT1, PS-BCP-m-HNT2, and PS-BCP-m-HNT5 (where 1, 2, and 5 correspond to the wt.% of HNTs). All nanocomposites depicted improved thermal degradation compared to the neat PS as revealed by thermogravimetric analysis (TGA). Transmission electron microscopy (TEM) confirmed the good dispersion state of HNTs and the importance of modification by SDS and BCP. X-ray diffraction (XRD) studies showed the characteristic interlayer spacing between the two silicate layers of pristine and modified HNTs. The PS/HNT nanocomposite films exhibited excellent ultraviolent-visible (UV-vis) absorbance properties and their potential application as UV-filters could be envisaged. © 2017 Lazaros Tzounis et al

The effect of noble metal (M: Ir, Pt, Pd) on M/Ce2 O3-\u3b3-Al2 O3 catalysts for hydrogen production via the steam reforming of glycerol

A promising route for the energetic valorisation of the main by-product of the biodiesel industry is the steam reforming of glycerol, as it can theoretically produce seven moles of H2 for every mole of C3 H8 O3. In the work presented herein, CeO2 \u2013Al2 O3 was used as supporting material for Ir, Pd and Pt catalysts, which were prepared using the incipient wetness impregnation technique and characterized by employing N2 adsorption\u2013desorption, X-Ray Diffraction (XRD), Temperature Programmed Reduction (TPR), Temperature Programmed Desorption (TPD), X-ray Photoelectron Spectroscopy (XPS) and Transmission Electron Microscopy (TEM). The catalytic experiments aimed at identifying the effect of temperature on the total conversion of glycerol, on the conversion of glycerol to gaseous products, the selectivity towards the gaseous products (H2, CO2, CO, CH4) and the determination of the H2 /CO and CO/CO2 molar ratios. The main liquid effluents produced during the reaction were quantified. The results revealed that the Pt/CeAl catalyst was more selective towards H2, which can be related to its increased number of Br\uf8nsted acid sites, which improved the hydrogenolysis and dehydrogenation\u2013dehydration of condensable intermediates. The time-on-stream experiments, undertaken at low Water Glycerol Feed Ratios (WGFR), showed gradual deactivation for all catalysts. This is likely due to the dehydration reaction, which leads to the formation of unsaturated hydrocarbon species and eventually to carbon deposition. The weak metal\u2013support interaction shown for the Ir/CeAl catalyst also led to pronounced sintering of the metallic particles

The influence of SiO2 doping on the Ni/ZrO2 supported catalyst for hydrogen production through the glycerol steam reforming reaction

The glycerol steam reforming (GSR) reaction for H2 production was studied comparing the performance of Ni supported on ZrO2 and SiO2-ZrO2 catalysts. The surface and bulk properties were determined by ICP, BET, XRD, TPD, TPR, TPO, XPS, SEM and STEM-HAADF. It was suggested that the addition of SiO2 stabilizes the ZrO2 monoclinic structure, restricts the sintering of nickel particles and strengthens the interaction between Ni2+ species and support. It also removes the weak acidic sites and increases the amount of the strong acidic sites, whereas it decreases the amount of the basic sites. Furthermore, it influences the gaseous products’ distribution by increasing H2 yield and not favouring the transformation of CO2 in CO. Thus, a high H2/CO ratio can be achieved accompanying by negligible value for CO/CO2. From the liquid products quantitative analysis, it was suggested that acetone and acetaldehyde were the main products for the Ni/Zr catalyst, for 750oC, whereas for the Ni/SiZr catalyst allyl alcohol was the only liquid product for the same temperature. It was also concluded that the Ni/SiZr sample seems to be more resistant to deactivation however, for both catalysts a substantial amount of carbon exists on the catalytic surface in the shape of carbon nanotubes and amorphous carbon

Cerium oxide catalysts for oxidative coupling of methane reaction: Effect of lithium, samarium and lanthanum dopants

The work presented herein reports on the oxidative coupling of methane (OCM) performance of a series of Li-free and Li-doped CeO2 and CeO2 modified with Sm3+ and La3+ catalysts. The supporting materials (Ce, Sm-Ce and La-Sm-Ce metal oxides) were synthesized using the microwave assisted sol-gel method in order to achieve nanophase complex materials with increased particle surface energy and reactivity. Lithium ions were added, using the wet impregnation technique, in order to further improve the physicochemical characteristics and reinforce the activity and selectivity, in terms of C2H6 and C2H4 production. All materials were characterized using N2 adsorption-desorption, XRD, Raman spectroscopy, CO2-TPD, H2-TPR, SEM and XPS. We showed that the addition of lithium species changed the reaction pathway and drastically enhanced the production of ethylene and ethane, mainly for the promoted catalysts (Li/Sm-Ce and Li/La-Sm-Ce). In particular, the presence and the synergy between the electrophilic oxygen species (peroxide and superoxide), population of oxygen vacancy sites and the surface moderate basic sites determined the reaction pathway and the desirable product distribution

Ni supported on CaO-MgO-Al 2 O 3 as a highly selective and stable catalyst for H 2 production via the glycerol steam reforming reaction

A comparative study of the GSR performance for Ni/CaO-MgO-Al2O3 and Ni/Al2O3 catalysts is reported. Catalysts were synthesized applying the wet impregnation method at a constant metal loading (8 wt %). Synthesized samples were characterized by N2 adsorption/desorption, ICP, BET, XRD, NH3-TPD, CO2-TPD, H2-TPR, XPS, TEM, STEM-HAADF and EDS. The carbon deposited on their surface under reaction conditions was characterized by TPO, Raman and TEM. It was proven that the use of CaO-MgO as alumina modifiers leads to smaller nickel species crystallite size, increased basicity and surface amount of Ni0 phase. Thus, it increases the conversion to gaseous products favoring H2 and CO2 production to the detriment of CO formation, by enhancing the water gas-shift (WGS) reaction. No liquid products were produced by the Ni/modAl catalyst over 550 °C, whereas time on stream results confirmed that deactivation can be prevented, as apart from decreasing the amount of coke deposition the nature of carbon was altered towards less graphitic and more defective structures

Effect of operating parameters on the selective catalytic deoxygenation of palm oil to produce renewable diesel over Ni supported on Al2O3, ZrO2 and SiO2 catalysts

The present work investigated the production of Green Diesel through the deoxygenation of palm oil over Ni catalysts supported on γ-Αl2O3, ZrO2 and SiO2 for a continuous flow fixed bed reactor. A comprehensive experimental study was carried out in order to examine the effects of temperature, pressure, LHSV and H2/oil feed ratio on catalytic activity during short (6 h) and long (20 h) time-on-stream experiments. The catalysts were prepared through the wet impregnation method (8 wt.% Ni) and were extensively characterized by N2 adsorption/desorption, XRD, NH3-TPD, CO2-TPD, H2-TPD, H2-TPR, XPS, TEM/HR-TEM and Raman. The characterization of the materials prior to reaction revealed that although relatively small Ni nanoparticles were achieved for all catalysts (4.3 ± 1.6 nm, 6.1 ± 1.8 nm and 6.0 ± 1.8 nm for the Ni/Al2O3, Ni/ZrO2 and Ni/SiO2 catalysts, respectively), NiO was better dispersed on the Ni/ZrO2 catalyst, while the opposite was true for the Ni/SiO2 sample. In the case of Ni/Al2O3, part of Ni could not participate in the reaction due to its entrapment in the NiAl2O4 spinel phase. Regarding performance, although an increase in H2 pressure led to increases in paraffin conversion, the increase of temperature was beneficial only up to a critical value which differed for each catalytic system under consideration (375 oC, 300 oC and 350 oC for the Ni/Al2O3, Ni/ZrO2 and Ni/SiO2 catalysts, respectively). All catalysts favored the deCO2 and deCO deoxygenation paths much more extensively than HDO, irrespective of testing conditions. Time-on-stream experiments showed that all catalysts deactivated after about 6 h, which was attributed to the sintering of the Ni particles and/or their covering by a thin graphitic carbon shell