Lignin is one of the main structural components of lignocellulosic biomass and can be utilized to produce phenolic compounds that can be converted downstream to cycloalkanes and aromatics, which are useful as drop-in road or aviation biofuels. Within this study, the hydrodeoxygenation of model phenolic/aromatic compounds and surrogate mixture simulating the light fraction of lignin fast-pyrolysis bio-oil was performed under mild reaction conditions. Ni/BEA zeolite was selected as a catalyst to investigate the conversion and the product selectivity of alkyl phenols (phenol, catechol, cresols), methoxy-phenols (guaiacol, syringol, creosol), aromatics (anisole, 1,2,3-trimethoxybenzene) and dimer (2-phenoxy-1-phenyl ethanol) compounds towards (alkyl)cycloalkanes. The hydrodeoxygenation of a surrogate mixture of eleven phenolic and aromatic compounds was then studied by investigating the effect of reaction conditions (temperature, time, H2 pressure, surrogate mixture concentration, and catalyst-to-feed ratio). The conversion of model compounds was in the range of 80–100%, towards a 37–81% (alkyl)cycloalkane yield, being strongly dependent on the complexity/side-chain group of the phenolic/aromatic ring. Regarding the hydrodeoxygenation of the surrogate mixture, 59–100% conversion was achieved, with up to a 72% yield of C6–C9 cycloalkanes. Characterization of spent catalysts showed that the hydrodeoxygenation of surrogate mixture led to carbonaceous depositions on the catalyst, which can be limited under lower temperatures and longer reaction conditions, while after regeneration, the physicochemical properties of catalysts can be partially recovered.
In the present work, the individual or synergistic effect of Ni-based catalysts (Ni/CeO2, Ni/Al2O3) and an eutectic carbonate salt mixture (MS) on the CO2 gasification performance of olive kernels was investigated. It was found that the Ni/CeO2 catalyst presented a relatively superior instant gasification reaction rate (Rco) compared to Ni/Al2O3, in line with the significant redox capability of CeO2. On the other hand, the use of the binary eutectic carbonate salt mixture (MS) lowered the onset and maximum CO2 gasification temperatures, resulting in a notably higher carbon conversion efficiency (81%) compared to the individual Ni-based catalysts and non-catalytic gasification tests (60%). Interestingly, a synergetic catalyst-carbonate salt mixture effect was revealed in the low and intermediate CO2 gasification temperature regimes, boosting the instant gasification reaction rate (Rco). In fact, in the temperature range of 300 to 550 °C, the maximum Rco value for both MS-Ni/Al2O3 and MS-Ni/CeO2 systems were four times higher (4 × 10−3 min−1 at 460 °C) compared to the individual counterparts. The present results demonstrated for the first time the combined effect of two different Ni-based catalysts and an eutectic carbonate salt mixture towards enhancing the CO production rate during CO2 gasification of olive kernel biomass fuel, especially in the devolatilization and tar cracking/reforming zones. On the basis of a systematic characterization study and lab-scale gasification experiments, the beneficial role of catalysts and molten carbonate salts on the gasification process was revealed, which can be ascribed to the catalytic activity as well as the improved mass and heat transport properties offered by the molten carbonate salts.
Controlled silica loading reduces zirconia particle size and tunes the Brønsted-to-Lewis acid balance, giving an optimum at intermediate SiO 2 content for efficient, hydrogen-free γ-valerolactone production via transfer hydrogenation.
The development of non-noble metal catalysts provides a cost-effective and sustainable route for glucose oxidation to gluconic acid. In this study, a series of catalysts based on inexpensive transition metals (Cr, Cu, Ni, Fe) and/or Au were synthesized using siliceous supports (SiO2 and MCM-41) and systematically evaluated. The aim was to partially or fully replace noble metals with lower-cost alternatives, while maintaining high catalytic performance. Comprehensive characterization—including ICP-AES for composition, N2 adsorption–desorption for porosity, XRD for structure, H2-TPR for reducibility, and NH3-TPD for acidity—was conducted to establish structure–property relationships. Among the tested catalysts, Ni- and Fe-based systems exhibited superior stability, with NiO/SiO2 achieving gluconic acid yields comparable to Au. The bimetallic Au–Ni/SiO2 catalyst displayed enhanced metal–support interactions and minimal leaching (<2%), while Au–Fe/SiO2 improved selectivity, yielding up to 23% gluconic acid, surpassing 5Fe/SiO2 (18%) and 0.3Au/SiO2 (15%), albeit with lower stability. These results highlight the potential of low-cost transition-metal and bimetallic catalysts as efficient and economically viable systems for selective glucose oxidation, providing insights for rational catalyst design in sustainable carbohydrate valorization.