Oxidation and pyrolysis of methane and methyl formate in a plug flow reactor: computational and experimenal studies

Biodiesel represents a possible substitute to the fossil fuels; for this reason a good comprehension of the kinetics involved is important. Due to the complexity of the biodiesel mixture a common practice is the use of surrogate molecules to study its reactivity. In this work are presented the experimental and computational results obtained for the oxidation and pyrolysis of methane and methyl formate conducted in a plug flow reactor. The work was divided into two parts: the first one was the setup assembly whilst, in the second one, was realized a comparison between the experimental and model results; these last was obtained using models available in literature. It was started studying the methane since, a validate model was available, in this way was possible to verify the reliability of the experimental results. After this first study the attention was focused on the methyl formate investigation. All the analysis were conducted at different temperatures, pressures and, for the oxidation, at different equivalence ratios. The results shown that, a good comprehension of the kinetics is reach but efforts are necessary to better evaluate kinetics parameters such as activation energy. The results even point out that the realized setup is adapt to study the oxidation and pyrolysis and, for this reason, it will be employed to study a longer chain esters with the aim to better understand the kinetic of the molecules that are part of the biodiesel mixture.

Biodiesel ottenuto da olio di babassu e sue miscele: studio di produzione e controllo di qualità

Il contributo all’innalzamento del riscaldamento globale, prodotto dai combustibili fossili è un dei principali problemi ambientali. Le bioenergie potrebbero contribuire enormemente alla riduzione di questo fenomeno, sostituendo in parte i combustibili tradizionali di origine fossile. In questo contesto, può collocarsi il biodiesel prodotto a partire da oli vegetali, rappresentando una valida e strategica alternativa. Il biodiesel è una miscela di metil esteri di acidi grassi, [fatty acids methyl esters (FAME)], normalmente ottenuta tramite reazione di transesterificazione tra oli vegetali e alcol a catena corta in presenza di un catalizzatore acido o basico in catalisi sia omogena che eterogenea. Il biodiesel si colloca tra le materie prime di seconda generazione e può risultare una buona base di partenza per ottenere un biodiesel performante e con un basso costo finale.

Synthesis of novel cobalt and iron complexes for sustainable catalytic hydrogenations

Aim of the present work of thesis is to synthesize new non-noble metal based complexes to be employ in redox reactions by a metal-ligand cooperative mechanism. The need of replacing toxic and expensive precious metal complexes with more available and benign metals, has led to the development of new compounds based on cobalt and iron, which are the metals investigated in this study. A carbonyl-tetrahydroborato-bis[(2-diisopropylphosphino)ethyl]amine-cobalt complex bearing a PNP-type ligand is synthesized by a three-step route. Optimization attempt of reaction route were assessed in order to lowering reaction times and solvent waste. New cobalt complex has been tested in esters hydrogenation as well as in acceptorless dehydrogenative coupling of ethanol. Other varieties of substrates were also tested in order to evaluate any possible applications. Concerning iron complex, dicarbonyl-(η4-3,4-bis(4-methoxyphenyl)-2,5-diphenylcyclopenta-2,4-dienone)(1,3-dimethyl-ilidene)iron is synthesized by a three steps route, involving transmetallation of a silver complex, derived from an imidazolium salt, to iron complex. In order to avoid solvent waste, optimization is assessed. Studies were performed to assess activity of triscarbonyl iron precursor toward imidazolium salt and silver complexes.

Studies towards the total synthesis of penicillipyrone b via a biomimetic approach

Pennicillipyrone A and B are two novel meroterpenoids isolated from the marine-derived fungus Penicilliump sp. Although a preliminary toxicity studies demonstrated the bioactivity of penicillipyrone A to be far superior to that of its congener penicillipyrone B, we were intrigued by its structure. Moreover, it appeared as though one could design an efficient total synthesis based on chemistry that was familiar to our laboratory. The purpose of this project was the study of a new synthesis of Pennicillipyrone B by way of a doubley-biomimetic approach. The intended approach proceeds through a polyene cascade reaction terminated by a nucleophilic pyrone - a reaction not yet known in the literature for the construction of this type of scaffold. During the course of this study we have learned about the unanticipated reactivity of C2 substituted keto-dioxinones with regard to self-condensation. In addition, four new compounds were synthesized and two synthetic routes to the target molecule are presented.