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Opis: In recent decades, there has been a growing interest in producing biofuels and biochemicals from renewable sources. Furfural stands as one of the ligno(hemi)cellulosic biomass derived platform chemical, which can be transformed into numerous value-added products. The goal of this PhD was to systematically study hydrotreatment reactions of furfural under varying operating conditions and to gain insights into the reaction mechanism and kinetics. An extensive experimental and computational study of hydrogenation, hydrodeoxygenation, oligomerisation and etherification of furfural in a three-phase batch reactor was performed. The goals were divided into three consecutive objectives. In the first part, hydrotreatment of furfural over Pd/C catalyst under various reaction conditions, including the solvent selection (solventless conditions, tetrahydrofuran, isopropanol), atmosphere (nitrogen, hydrogen), temperature (100–200 °C), pressure (25–75 bar) and stirring speed, was studied. A reaction pathway network and a micro-kinetic model were developed, incorporating thermodynamics (hydrogen solubility), mass transfer, adsorption, desorption, and surface reactions. These phenomena and their contribution to the surface coverages, TOF’s and global reaction rates were studied. The hydrogen presence on the catalyst surface was found to influence the main reaction pathway, leading to ring, aldehyde group or full hydrogenation. In the second part, various monometallic catalysts (Pd/C, Pt/C, Re/C, Ru/C, Rh/C, Ni/C, Cu/C) were tested at 100 -200 °C with 60 bar of hydrogen and tetrahydrofuran as solvent. A generalized reaction pathway network was developed. H2 temperature-programmed reduction (H2-TPR) and CO temperature-programmed desorption (CO-TPD) were conducted, and a regression analysis of the results was subsequently performed by numerical modelling and optimisation. The obtained adsorption and desorption kinetic parameters for active metallic sites were further used in a generalized micro-kinetic model, applicable to all tested catalysts. Pd/C exhibited high activity and non-selective hydrogenation of furfural, while other catalysts showed selective aldehyde group hydrogenation followed by deoxygenation, consistent with density functional theory (DFT) calculations. Ru/C uniquely produced 2 methyltetrahydrofuran and ring-opening products at 200 °C. In silico optimization of reaction conditions for promising catalysts ((Pd/C, Pt/C, Re/C, Ni/C) aimed to maximize the yield of the target product. In the third part, the influence of support on catalytic activity was studied. Hydrotreatment of furfural over Pd/Al2O3, Pd/SiO2, Ru/Al2O3, Ru/SiO2, Ni/Al2O3, and Ni/SiO2 was performed between 150 - 200 °C, using 60 bar of hydrogen and tetrahydrofuran as solvent. The strength and rate of adsorption and desorption to/from acidic, metallic and interface site structures were determined, using H2-TPR, CO-TPD and NH3-TPD and subsequent regression analysis of the results by numerical modelling and optimisation. The resulting parameters were sequentially used in the generalized micro-kinetic model to quantify the contribution of the active metal (Ni, Pd, or Ru), support (Al2O3 or SiO2), interphase sites and their relationship on catalyst activity and selectivity. Evaluation of morphological and structural characteristics, adsorption/desorption and intrinsic reaction kinetics has indicated that the coverage of acidic sites (on alumina or silica) facilitated yielding ring hydrogenation and inhibited deoxygenation, decarbonylation and cyclic compound opening. The rates for aromatics or aldehyde functional groups were, nonetheless, affected in a different order. The used and developed methods and findings of this PhD offer useful guidelines for transforming furfural into high-value chemicals through catalytic hydrotreatment, with significant implications for future research and industrial applications.
Ključne besede: lignocellulosic biomass, furfural, catalytic hydrogenation, micro-kinetic mass transfer model, reaction kinetics, first-principle methods, furfuryl alcohol, tetrahydrofurfuryl alcoholv, dissertations
Objavljeno v RUNG: 08.11.2024; Ogledov: 292; Prenosov: 4
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Ključne besede: X-Ray Raman, Na-ion batteries
Objavljeno v RUNG: 05.07.2024; Ogledov: 960; Prenosov: 3
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Opis: Abstract. Recent years have seen an increase in the use of wood for energy production of over 30 %, and this trend is expected to continue due to the current energy crisis and geopolitical instability. At present, residential wood burning (RWB) is one of the most important sources of organic aerosols (OA) and black carbon (BC). While BC is recognized for its large light absorption cross-section, the role of OA in light absorption is still under evaluation due to their heterogeneous composition and source-dependent optical properties. Studies that characterize wood-burning aerosol emissions in Europe typically focus on urban and background sites and only cover BC properties. However, RWB is more prevalent in rural areas, and the present scenario indicates that an improved understanding of the RWB aerosol optical properties and their subsequent connection to climate impacts is necessary for rural areas. We have characterized atmospheric aerosol particles from a central European rural site during wintertime in the village of Retje in Loški Potok, Slovenia, from 01.12.2017 to 07.03.2018. The village experienced extremely high aerosol concentrations produced by RWB and near-ground temperature inversion. The isolated location of the site and the substantial local emissions made it an ideal laboratory-like place for characterizing RWB aerosols with low influence from non-RWB sources under ambient conditions. The mean mass concentrations of OA and BC were 34.8 µg m-3 (max = 271.8 µg m-3) and 3.1 µg m-3 (max = 24.3 µg m-3), respectively. The mean total particle number concentration (10–600 nm) was 9.9 x 103 particles cm-3 (max = 53.5 x 103 particles cm-3). The mean total light absorption coefficient at 370 nm and 880 nm measured by an Aethalometer AE33 were 122.8 Mm-1 and 15.3 Mm-1 and had maximum values of 1103.9 Mm-1 and 179.1 Mm-1, respectively. The aerosol concentrations and absorption coefficients measured during the campaign in Loški Potok were significantly larger than those reported values for several urban areas in the region with larger populations and extent of aerosol sources. Here, considerable contributions from brown carbon (BrC) to the total light absorption were identified, reaching up to 60 % and 48 % in the near UV (370 nm) and blue (470 nm) wavelengths. These contributions are up to three times higher than values reported for other sites impacted by wood-burning emissions. The calculated mass absorption cross-section and the absorption Ångström exponent for RWB OA were MACOA, 370 nm= 2.4 m2 g-1, and AAEBrC, 370–590 nm= 3.9, respectively. Simple forcing efficiency (SFE) calculations were performed as a sensitivity analysis to evaluate the climate impact of the RWB aerosols produced at the study site by integrating the optical properties measured during the campaign. The SFE results show a considerable forcing capacity from the local RWB aerosols, with a high sensitivity to OA absorption properties and a more substantial impact over bright surfaces like snow, typical during the coldest season with higher OA emissions from RWB. Our study's results are highly significant regarding air pollution, optical properties, and climate impact. The findings suggest that there may be an underestimation of RWB emissions in rural Europe and that further investigation is necessary.
Ključne besede: wood-burning aerosols, optical characterization, black carbon, rural areas
Objavljeno v RUNG: 10.01.2024; Ogledov: 1832; Prenosov: 11
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Ključne besede: local air quality, aerosol measurements, perception, heating habits
Objavljeno v RUNG: 27.02.2023; Ogledov: 2404; Prenosov: 0
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Ključne besede: information security, cybersecurity, network security, passwords, physical security, backup, encryption, data wiping, VPN, anonymization
Objavljeno v RUNG: 30.08.2022; Ogledov: 1984; Prenosov: 42
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