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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: 324; Prenosov: 5
Celotno besedilo (9,22 MB)

Opis: The Auger Radio Detector (RD) will increase the sky coverage and overall aperture for mass- sensitive measurements of ultra-high-energy cosmic rays with the Pierre Auger Observatory. The installation of over 1600 dual-polarized short aperiodic loaded loop antennas (SALLAs) on an area of about 3000 sq. km will enable the detection of highly inclined air showers via the emitted electromagnetic radiation in coincidence with the Auger water-Cherenkov detector array (SD). The combination of complementary information from both detectors yields a strong sensitivity to the mass composition of cosmic rays. We will present the expected performance of the RD to detect and reconstruct inclined air showers. This study features comprehensive sets of Monte-Carlo generated air showers, utilizes a complete description of the instrumental response of the radio antennas, and in-situ recorded background. The estimation of an energy- and direction-dependent aperture yields an expectation of about 3900 events with energies above 10[sup]19 eV being detected during 10 years of operation. From a full event reconstruction, we quantify the achievable energy resolution to be better than 10% at and beyond 10[sup]19 eV. With this at hand, the potential to measure the number of muons and discriminate between different cosmic-ray primaries in combination with the SD using inclined air showers is presented. The discrimination between proton- and iron-induced air showers yields a figure-of-merit of 1.6.
Ključne besede: Pierre Auger Observatory, ultra-high-energy cosmic rays, extensive air showers, Auger Radio Detector, Auger water-Cherenkov detector array, mass-sensitive UHECR measurements
Objavljeno v RUNG: 03.10.2024; Ogledov: 473; Prenosov: 6
Celotno besedilo (917,68 KB)
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Opis: Similarities and differences in the submicron atmospheric aerosol chemical composition are analyzed from a unique set of measurements performed at 21 sites across Europe for at least one year. These sites are located between 35 and 62°N and 10° W – 26°E, and represent various types of settings (remote, coastal, rural, industrial, urban). Measurements were all carried out on-line with a 30-min time resolution using mass spectroscopy based instruments known as Aerosol Chemical Speciation Monitors (ACSM) and Aerosol Mass Spectrometers (AMS) and following common measurement guidelines. Data regarding organics, sulfate, nitrate and ammonium concentrations, as well as the sum of them called non-refractory submicron aerosol mass concentration ([NR-PM1]) are discussed. NR-PM1 concentrations generally increase from remote to urban sites. They are mostly larger in the mid-latitude band than in southern and northern Europe. On average, organics account for the major part (36–64%) of NR-PM1 followed by sulfate (12–44%) and nitrate (6–35%). The annual mean chemical composition of NR-PM1 at rural (or regional background) sites and urban background sites are very similar. Considering rural and regional background sites only, nitrate contribution is higher and sulfate contribution is lower in mid-latitude Europe compared to northern and southern Europe. Large seasonal variations in concentrations (μg/m³) of one or more components of NR-PM1 can be observed at all sites, as well as in the chemical composition of NR-PM1 (%) at most sites. Significant diel cycles in the contribution to [NR-PM1] of organics, sulfate, and nitrate can be observed at a majority of sites both in winter and summer. Early morning minima in organics in concomitance with maxima in nitrate are common features at regional and urban background sites. Daily variations are much smaller at a number of coastal and rural sites. Looking at NR-PM1 chemical composition as a function of NR-PM1 mass concentration reveals that although organics account for the major fraction of NR-PM1 at all concentration levels at most sites, nitrate contribution generally increases with NR-PM1 mass concentration and predominates when NR-PM1 mass concentrations exceed 40 μg/m³ at half of the sites.
Ključne besede: aerosol, chemical composition, mass spectrometry, phenomenology
Objavljeno v RUNG: 10.05.2024; Ogledov: 982; Prenosov: 5
Celotno besedilo (9,75 MB)
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Opis: The combined interpretation of the spectrum and composition measurements plays a key role in the quest for the origin of ultra-high-energy cosmic rays (UHECRs). The Pierre Auger Observatory, thanks to its huge exposure, provides the most precise measurement of the energy spectrum of UHECRs and the most reliable information on their composition, exploiting the distributions of the depth of maximum of the showers in the atmosphere. A combined fit of a simple astrophysical model of UHECR sources to the spectrum and mass composition measurements is used to evaluate the constraining power of the data measured by the Pierre Auger Observatory on the source properties. We find that our data across the “ankle” feature are well reproduced if two extragalactic populations of sources are considered, one emitting a very soft spectrum which dominates the region below the ankle, and the other taking over at energies above the ankle, with an intermediate mixed composition, a hard spectrum and a low rigidity cutoff. Interestingly, similar results can also be obtained if the medium-mass contribution at lower energy is provided by an additional galactic component.
Ključne besede: Pierre Auger Observatory, ultra-high energy cosmic rays, UHECR energy spectrum, UHECR mass composition
Objavljeno v RUNG: 24.01.2024; Ogledov: 2128; Prenosov: 10
Celotno besedilo (381,66 KB)
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Opis: The measurements by the Pierre Auger Observatory of the energy spectrum and mass composition of cosmic rays can be interpreted assuming the presence of two extragalactic source populations, one dominating the flux at energies above a few EeV and the other below. To fit the data ignoring magnetic field effects, the high-energy population needs to accelerate a mixture of nuclei with very hard spectra, at odds with the approximate �−2 shape expected from diffusive shock acceleration. The presence of turbulent extragalactic magnetic fields in the region between the closest sources and the Earth can significantly modify the observed CR spectrum with respect to that emitted by the sources, reducing the flux of low-rigidity particles that reach the Earth. We here take into account this magnetic horizon effect in the combined fit of the spectrum and shower depth distributions, exploring the possibility that a spectrum for the high-energy population sources with a shape closer to �^(−2) be able to explain the observations. We find that a large inter-source separation �s and a large magnetic field RMS amplitude within the Local Supercluster region, such that �rms ≃ 100 nG (40 Mpc/�s) √︁25 kpc/�coh, are needed to interpret the data within this scenario, where �coh is the magnetic field coherence length.
Ključne besede: ultra-high energy cosmic rays, Pierre Auger Observatory, mass composition, extragalactic magnetic fiels
Objavljeno v RUNG: 22.01.2024; Ogledov: 1380; Prenosov: 7
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