The synthesis of maleic anhydride: study of a new process and improvement of the industrial catalyst

Maleic anhydride is an important chemical intermediate mainly produced by the selective oxidation of n-butane, an industrial process catalyzed by vanadyl pyrophosphate-based materials, (VO)2P2O7. The first topic was investigated in collaboration with a company specialized in the production of organic anhydrides (Polynt SpA), with the aim of improving the performance of the process for the selective oxidation of n-butane to maleic anhydride, comparing the behavior of an industrial vanadyl pyrophosphate catalysts when utilized either in the industrial plant or in lab-scale reactor. The study was focused on how the catalyst characteristics and reactivity are affected by the reaction conditions and how the addition of a dopant can enhance the catalytic performance. Moreover, the ageing of the catalyst was studied, in order to correlate the deactivation process with the modifications occurring in the catalyst. The second topic was produced within the Seventh Framework (FP7) European Project “EuroBioRef”. The study was focused on a new route for the synthesis of maleic anhydride starting from an alternative reactant produced by fermentation of biomass:“bio-1-butanol”. In this field, the different possible catalytic configurations were investigated: the process was divided into two main reactions, the dehydration of 1-butanol to butenes and the selective oxidation of butenes to maleic anhydride. The features needed to catalyze the two steps were analyzed and different materials were proposed as catalysts, namely Keggin-type polyoxometalates, VOPO4∙2H2O and (VO)2P2O7. The reactivity of 1-butanol was tested under different conditions, in order to optimize the performance and understand the nature of the interaction between the alcohol and the catalyst surface. Then, the key intermediates in the mechanism of 1-butanol oxidehydration to MA were studied, with the aim of understanding the possible reaction mechanism. Lastly, the reactivity of the chemically sourced 1-butanol was compared with that one of different types of bio-butanols produced by biomass fermentation.

The rupture process of recent tsunamigenic earthquakes by geophysical data inversion

Subduction zones are the favorite places to generate tsunamigenic earthquakes, where friction between oceanic and continental plates causes the occurrence of a strong seismicity. The topics and the methodologies discussed in this thesis are focussed to the understanding of the rupture process of the seismic sources of great earthquakes that generate tsunamis. The tsunamigenesis is controlled by several kinematical characteristic of the parent earthquake, as the focal mechanism, the depth of the rupture, the slip distribution along the fault area and by the mechanical properties of the source zone. Each of these factors plays a fundamental role in the tsunami generation. Therefore, inferring the source parameters of tsunamigenic earthquakes is crucial to understand the generation of the consequent tsunami and so to mitigate the risk along the coasts. The typical way to proceed when we want to gather information regarding the source process is to have recourse to the inversion of geophysical data that are available. Tsunami data, moreover, are useful to constrain the portion of the fault area that extends offshore, generally close to the trench that, on the contrary, other kinds of data are not able to constrain. In this thesis I have discussed the rupture process of some recent tsunamigenic events, as inferred by means of an inverse method. I have presented the 2003 Tokachi-Oki (Japan) earthquake (Mw 8.1). In this study the slip distribution on the fault has been inferred by inverting tsunami waveform, GPS, and bottom-pressure data. The joint inversion of tsunami and geodetic data has revealed a much better constrain for the slip distribution on the fault rather than the separate inversions of single datasets. Then we have studied the earthquake occurred on 2007 in southern Sumatra (Mw 8.4). By inverting several tsunami waveforms, both in the near and in the far field, we have determined the slip distribution and the mean rupture velocity along the causative fault. Since the largest patch of slip was concentrated on the deepest part of the fault, this is the likely reason for the small tsunami waves that followed the earthquake, pointing out how much the depth of the rupture plays a crucial role in controlling the tsunamigenesis. Finally, we have presented a new rupture model for the great 2004 Sumatra earthquake (Mw 9.2). We have performed the joint inversion of tsunami waveform, GPS and satellite altimetry data, to infer the slip distribution, the slip direction, and the rupture velocity on the fault. Furthermore, in this work we have presented a novel method to estimate, in a self-consistent way, the average rigidity of the source zone. The estimation of the source zone rigidity is important since it may play a significant role in the tsunami generation and, particularly for slow earthquakes, a low rigidity value is sometimes necessary to explain how a relatively low seismic moment earthquake may generate significant tsunamis; this latter point may be relevant for explaining the mechanics of the tsunami earthquakes, one of the open issues in present day seismology. The investigation of these tsunamigenic earthquakes has underlined the importance to use a joint inversion of different geophysical data to determine the rupture characteristics. The results shown here have important implications for the implementation of new tsunami warning systems – particularly in the near-field – the improvement of the current ones, and furthermore for the planning of the inundation maps for tsunami-hazard assessment along the coastal area.

Methodological improvement of 3D fluoroscopic analysis for the robust quantification of 3D kinematics of human joints

3D video-fluoroscopy is an accurate but cumbersome technique to estimate natural or prosthetic human joint kinematics. This dissertation proposes innovative methodologies to improve the 3D fluoroscopic analysis reliability and usability. Being based on direct radiographic imaging of the joint, and avoiding soft tissue artefact that limits the accuracy of skin marker based techniques, the fluoroscopic analysis has a potential accuracy of the order of mm/deg or better. It can provide fundamental informations for clinical and methodological applications, but, notwithstanding the number of methodological protocols proposed in the literature, time consuming user interaction is exploited to obtain consistent results. The user-dependency prevented a reliable quantification of the actual accuracy and precision of the methods, and, consequently, slowed down the translation to the clinical practice. The objective of the present work was to speed up this process introducing methodological improvements in the analysis. In the thesis, the fluoroscopic analysis was characterized in depth, in order to evaluate its pros and cons, and to provide reliable solutions to overcome its limitations. To this aim, an analytical approach was followed. The major sources of error were isolated with in-silico preliminary studies as: (a) geometric distortion and calibration errors, (b) 2D images and 3D models resolutions, (c) incorrect contour extraction, (d) bone model symmetries, (e) optimization algorithm limitations, (f) user errors. The effect of each criticality was quantified, and verified with an in-vivo preliminary study on the elbow joint. The dominant source of error was identified in the limited extent of the convergence domain for the local optimization algorithms, which forced the user to manually specify the starting pose for the estimating process. To solve this problem, two different approaches were followed: to increase the optimal pose convergence basin, the local approach used sequential alignments of the 6 degrees of freedom in order of sensitivity, or a geometrical feature-based estimation of the initial conditions for the optimization; the global approach used an unsupervised memetic algorithm to optimally explore the search domain. The performances of the technique were evaluated with a series of in-silico studies and validated in-vitro with a phantom based comparison with a radiostereometric gold-standard. The accuracy of the method is joint-dependent, and for the intact knee joint, the new unsupervised algorithm guaranteed a maximum error lower than 0.5 mm for in-plane translations, 10 mm for out-of-plane translation, and of 3 deg for rotations in a mono-planar setup; and lower than 0.5 mm for translations and 1 deg for rotations in a bi-planar setups. The bi-planar setup is best suited when accurate results are needed, such as for methodological research studies. The mono-planar analysis may be enough for clinical application when the analysis time and cost may be an issue. A further reduction of the user interaction was obtained for prosthetic joints kinematics. A mixed region-growing and level-set segmentation method was proposed and halved the analysis time, delegating the computational burden to the machine. In-silico and in-vivo studies demonstrated that the reliability of the new semiautomatic method was comparable to a user defined manual gold-standard. The improved fluoroscopic analysis was finally applied to a first in-vivo methodological study on the foot kinematics. Preliminary evaluations showed that the presented methodology represents a feasible gold-standard for the validation of skin marker based foot kinematics protocols.

Applicability of Process Mining Techniques in Business Environments

This thesis analyses problems related to the applicability, in business environments, of Process Mining tools and techniques. The first contribution is a presentation of the state of the art of Process Mining and a characterization of companies, in terms of their "process awareness". The work continues identifying circumstance where problems can emerge: data preparation; actual mining; and results interpretation. Other problems are the configuration of parameters by not-expert users and computational complexity. We concentrate on two possible scenarios: "batch" and "on-line" Process Mining. Concerning the batch Process Mining, we first investigated the data preparation problem and we proposed a solution for the identification of the "case-ids" whenever this field is not explicitly indicated. After that, we concentrated on problems at mining time and we propose the generalization of a well-known control-flow discovery algorithm in order to exploit non instantaneous events. The usage of interval-based recording leads to an important improvement of performance. Later on, we report our work on the parameters configuration for not-expert users. We present two approaches to select the "best" parameters configuration: one is completely autonomous; the other requires human interaction to navigate a hierarchy of candidate models. Concerning the data interpretation and results evaluation, we propose two metrics: a model-to-model and a model-to-log. Finally, we present an automatic approach for the extension of a control-flow model with social information, in order to simplify the analysis of these perspectives. The second part of this thesis deals with control-flow discovery algorithms in on-line settings. We propose a formal definition of the problem, and two baseline approaches. The actual mining algorithms proposed are two: the first is the adaptation, to the control-flow discovery problem, of a frequency counting algorithm; the second constitutes a framework of models which can be used for different kinds of streams (stationary versus evolving).

Improvement of photon transport model by including coupled photon-electron transport and kernel refinement

The first part of this work deals with the inverse problem solution in the X-ray spectroscopy field. An original strategy to solve the inverse problem by using the maximum entropy principle is illustrated. It is built the code UMESTRAT, to apply the described strategy in a semiautomatic way. The application of UMESTRAT is shown with a computational example. The second part of this work deals with the improvement of the X-ray Boltzmann model, by studying two radiative interactions neglected in the current photon models. Firstly it is studied the characteristic line emission due to Compton ionization. It is developed a strategy that allows the evaluation of this contribution for the shells K, L and M of all elements with Z from 11 to 92. It is evaluated the single shell Compton/photoelectric ratio as a function of the primary photon energy. It is derived the energy values at which the Compton interaction becomes the prevailing process to produce ionization for the considered shells. Finally it is introduced a new kernel for the XRF from Compton ionization. In a second place it is characterized the bremsstrahlung radiative contribution due the secondary electrons. The bremsstrahlung radiation is characterized in terms of space, angle and energy, for all elements whit Z=1-92 in the energy range 1–150 keV by using the Monte Carlo code PENELOPE. It is demonstrated that bremsstrahlung radiative contribution can be well approximated with an isotropic point photon source. It is created a data library comprising the energetic distributions of bremsstrahlung. It is developed a new bremsstrahlung kernel which allows the introduction of this contribution in the modified Boltzmann equation. An example of application to the simulation of a synchrotron experiment is shown.