Chemical recycling of municipal packaging waste by pyrolysis

[EN]The present doctoral thesis centers on studying pyrolysis as a chemical recycling technique for rejected packaging waste fractions coming from separation and sorting plants. The pyrolysis experiments have been carried out in a lab-scale installation equipped with a 3.5 L semi-batch reactor and a condensation and collection system for the liquids and gases generated. In the present thesis, an experimental study on the conventional pyrolysis process applied to the aforementioned waste fractions has been conducted, as well as the study of non-conventional or advanced pyrolysis processes such as catalytic and stepwise pyrolysis. The study of the operating parameters has been carried out using a mixed plastics simulated sample, the composition of which is similar to that found in real fractions, and subsequently the optimized process has been applied to real packaging waste. An exhaustive characterization of the solids, liquids and gases obtained in the process has been made after each experiment and their potential uses have been established. Finally, an empirical model that will predict the pyrolysis yields (% organic liquid, % aqueous liquid, % gases, % char, % inorganic solid) as a function of the composition of the initial sample has been developed. As a result of the experimental work done, the requirements have been established for an industrial packaging waste pyrolysis plant that aims to be sufficiently versatile as to generate useful products regardless of the nature of the raw material.

Tracking the evolution of waste recycling research using overlay maps of science

Tracking the evolution of research in waste recycling science (WRS) can be valuable for environmental agencies, as well as for recycling businesses. Maps of science are visual, easily readable representations of the cognitive structure of a branch of science, a particular area of research or the global spectrum of scientific production. They are generally built upon evidence collected from reliable sources of information, such as patent and scientific publication databases. This study uses the methodology developed by Rafols et al. (2010) to make a “double overlay map” of WRS upon a basemap reflecting the cognitive structure of all journal-published science, for the years 2005 and 2010. The analysis has taken into account the cognitive areas where WRS articles are published and the areas from where it takes its intellectual nourishing, paying special attention to the growing trends of the key areas. Interpretation of results lead to the conclusion that extraction of energy from waste will probably be an important research topic in the future, along with developments in general chemistry and chemical engineering oriented to the recovery of valuable materials from waste. Agricultural and material sciences, together with the combined economics, politics and geography field, are areas with which WRS shows a relevant and ever increasing cognitive relationship.

Application of a new pelletised organic bed for tex biodegradation in conventional biofilters

La problemática de las emisiones de gases contaminados generadas por las actividades humanas ha obligado al desarrollo de distintas tecnologías de tratamiento cuyo objetivo es minimizar el efecto de las mismas sobre el medio ambiente.La biofiltración es una de estas tecnologías de bajo coste que además es respetuosa con el entorno. Básicamente consiste en hacer pasar un gas contaminado a través de un medio poroso donde anida la biomasa que lleva a cabo la degradación de los contaminantes, generando productos no nocivos. El presente estudio se ha centrado en aportar soluciones a una de las principales limitaciones que presentan estos sistemas biológicos: el excesivo tiempo empleado por la biomasa para adaptarse a los contaminantes y degradarlos eficazmente.Se ha desarrollado una sistemática de aclimatación que ha permitido acortar el tiempo de adaptación de la biomasa específica para la eliminación de compuestos orgánicos volátiles (COVs). Estos compuestos, más específicamente los TEX (tolueno, p-xileno y etilbenceno), son uno de los grupos de contaminantes más habituales a nivel industrial, e incluso en ambientes interiores. La optimización de los parámetros de operación que afectan a esta tecnología (el nivel de humedad del soporte, temperatura, la interacción de varios contaminantes presentes en la misma corriente gaseosa, entre otros), ha llevado a la consecución de eficacias de depuración muy elevadas en el biotratamiento en continuo de corrientes gaseosas contaminadas.

Assessment of phytostabilization of Pb/Zn mine soils with organic amendments and a native metallicolous ecotype of Festuca Rubra l.: implications for amendment selection and recovery of soil health

La contaminación del suelo es una de las principales amenazas para los ecosistemas y la salud humana. Actualmente, desde un punto de vista tanto económico como ambiental, la fitoestabilización es la mejor tecnología para remediar suelos contaminados con elevadas concentraciones de metales como son los suelos mineros. La fitoestabilización asistida consiste en el empleo de plantas y enmiendas orgánicas y/o inorgánicas con el fin de reducir la movilidad y la biodisponibilidad de los contaminantes y recuperar la salud de suelo. En este trabajo se han realizado ensayos en microcosmos y en campo centrándonos en la salud del suelo minero contaminado con Pb y Zn durante un proceso de fitoestabilización empleando enmiendas orgánicas (purines vacunos, gallinaza, estiércol de oveja y lodos de papelera mezclados con gallinaza) y/o la especie metalífera Festuca rubra con el objetivo de (i) estudiar las interacciones suelo-enmienda responsables de los cambios inducidos por el proceso de quimioestabilización en las propiedades físicoquímicas y biológicas del suelo, (ii) evaluar la efectividad del proceso de fitoestabilización sobre suelos vegetados y de la revegetación sobre suelos desnudos (iii) valorar la idoneidad de distintos indicadores químicos y biológicos (parámetros microbianos y de la vegetación) para monitorizar la efectividad de la fitoestabilización asistida en términos de reducción de la biodisponibilidad de metales en el suelo, mejora de la vegetación y de la recuperación de la salud del suelo. La aplicación de enmiendas al suelo minero supone una entrada de materia orgánica y nutrientes que conduce a una disminución de la biodisponibilidad de metales, facilitando la colonización de las plantas y el crecimiento de la vegetación nativa, además de estimular la actividad microbiana del suelo. El pH del suelo es un factor crítico que condiciona la movilidad de los metales y la toxicidad del suelo. Las poblaciones microbianas de las enmiendas no modificaron la diversidad funcional de las comunidades microbianas nativas de la mina. Los purines vacunos y los lodos de papelera mezclados con gallinaza son los tratamientos más efectivos en el proceso de fitoestabilización asistida bajo condiciones de campo. La gallinaza fue el tratamiento que más estimuló el crecimiento de la vegetación nativa y la colonización en los suelos desnudos. El bioensayo de elongación radical de lechuga es un test sensible, sencillo y barato para evaluar la biodisponibilidad de metal y la ecotoxicidad del suelo. Los tocoferoles son biomarcadores de exposición a metales con potencial para su implementación en bioensayos de toxicidad. Este trabajo permite concluir que la población metalífera de F. rubra, combinada con enmiendas orgánicas, es una excelente candidata para los proyectos de fitoestabilización asistida. Además, la monitorización simultánea de los parámetros fisicoquímicos y microbiológicos del suelo y de su ecotoxicidad permite una evaluación adecuada de la salud del suelo, así como la selección de enmiendas apropiadas para el desarrollo de un proceso fitoestabilizador.

Optimization of solution-processed oligothiophene:fullerene based organic solar cells by using solvent additives

The optimization of solution-processed organic bulk-heterojunction solar cells with the acceptor-substituted quinquethiophene DCV5T-Bu-4 as donor in conjunction with PC61BM as acceptor is described. Power conversion efficiencies up to 3.0% and external quantum efficiencies up to 40% were obtained through the use of 1-chloronaphthalene as solvent additive in the fabrication of the photovoltaic devices. Furthermore, atomic force microscopy investigations of the photoactive layer gave insight into the distribution of donor and acceptor within the blend. The unique combination of solubility and thermal stability of DCV5T-Bu-4 also allows for fabrication of organic solar cells by vacuum deposition. Thus, we were able to perform a rare comparison of the device characteristics of the solution-processed DCV5T-Bu-4:PC61BM solar cell with its vacuum-processed DCV5T-Bu-4:C-60 counterpart. Interestingly in this case, the efficiencies of the small-molecule organic solar cells prepared by using solution techniques are approaching those fabricated by using vacuum technology. This result is significant as vacuum-processed devices typically display much better performances in photovoltaic cells. Keywords

Polymer-Optical-Fiber Lasers and Amplifiers Doped with Organic Dyes

Polymer optical fibers (POFs) doped with organic dyes can be used to make efficient lasers and amplifiers due to the high gains achievable in short distances. This paper analyzes the peculiarities of light amplification in POFs through some experimental data and a computational model capable of carrying out both power and spectral analyses. We investigate the emission spectral shifts and widths and on the optimum signal wavelength and pump power as functions of the fiber length, the fiber numerical aperture and the radial distribution of the dopant. Analyses for both step-index and graded-index POFs have been done.

STM study on the self-assembly of oligothiophene-based organic semiconductors

The self-assembly properties of a series of functionalized regioregular oligo(3-alkylthiophenes) were investigated by using scanning tunneling microscopy (STM) at the liquid-solid interface under ambient conditions. The characteristics of the 2-D crystals formed on the (0001) plane of highly ordered pyrolitic graphite (HOPG) strongly depend on the length of the p-conjugated oligomer backbone, on the functional groups attached to it, and on the alkyl substitution pattern on the individual thiophene units. Theoretical calculations were performed to analyze the geometry and electronic density of the molecular orbitals as well as to analyze the intermolecular interactions, in order to obtain models of the 2-D molecular ordering on the substrate.

Optimization of Organic-Inorganic Inter-phase in Hybrid Systems Based on Waterborne Polyurethanes and Silica Nanostructures

215 p.

Beta-Hydroxyimino Phosphorus Derivatives. An Efficient Tool in Organic Synthesis

[EN] The purpose of this review article is to illustrate synthetic aspects of functionalized phosphorus derivatives containing an oximo moiety at the beta-position. First section will be focused on the synthesis of phosphine oxides, phosphonates or phosphonium salts containing an oxime group. The synthesis of these derivatives comprises the carbon–phosphorus single bond construction by reaction of haloximes with phosphorus derivatives, nucleophilic addition of phosphorus reagents to carbonyl compounds, or nucleophilic addition of phosphorus reagents to nitro olefins. This section will also concentrate on the most practical routes for the synthesis of the target compounds, through carbon–nitrogen double bond formation, which are as follows: condensation processes of carbonyl compounds and hydroxylamine derivatives or addition of hydroxylamines to allenes or alkynes. The preparative use of beta-oximo phosphorus derivatives as synthetic intermediates will be discussed in a second section, comprising olefination reaction, oxidation of oximes to nitrile oxides by reaction at the C-N double bond of the oxime moiety, oxidation of these substrates to nitrosoalkenes, reduction to the corresponding hydroxylamines and some reactions at the hydroxyl group of the hydroxyimino moiety.

Systematic Studies on 3d- and 4f-Metal Containing Polyoxometalates Suitable for Organic Derivatization

232 p.

HYBRID PHOTOVOLTAIC DEVICES BASED ON ORGANIC SEMICONDUCTING POLYMERS AND INORGANIC NANOSTRUCTURED ELECTRODES

La fotovoltaica orgánica es una tecnología solar emergente que todavía no ha entrado en el mercado. El objetivo de esta tesis ha sido acercar un poco más la industrialización de dicha tecnología mediante el incremento de la eficiencia y la durabilidad de estos dispositivos solares. Para la consecución de dicho objetivo se identificaron las limitaciones existentes y se diseñó una hora de ruta con diversas estrategias para poder superar cada uno de los problemas. Así, mediante un exhaustivo control de la nano morfología del film fotoactivo y la introducción de electrodos nanoestructurados se ha conseguido incrementar la eficiencia. La sustitución de los electrodos estándares por nuevos electrodos basados en óxidos metálicos confiere durabilidad al sistema. Por último, la sustitución del óxido de indio y estaño como electrodo transparente por nanohilos metálicos de plata habilita la posibilidad de fabricar dispositivos solares flexibles de bajo coste.

The effect of low solubility organic acids on the hygroscopicity of sodium halide aerosols

In order to accurately assess the influence of fatty acids on the hygroscopic and other physicochemical properties of sea salt aerosols, hexanoic, octanoic or lauric acid together with sodium halide salts (NaCl, NaBr and NaI) have been chosen to be investigated in this study. The hygroscopic properties of sodium halide sub-micrometre particles covered with organic acids have been examined by Fourier-transform infrared spectroscopy in an aerosol flow cell. Covered particles were generated by flowing atomized sodium halide particles (either dry or aqueous) through a heated oven containing the gaseous acid. The obtained results indicate that gaseous organic acids easily nucleate onto dry and aqueous sodium halide particles. On the other hand, scanning electron microscopy (SEM) images indicate that lauric acid coating on NaCl particles makes them to aggregate in small clusters. The hygroscopic behaviour of covered sodium halide particles in deliquescence mode shows different features with the exchange of the halide ion, whereas the organic surfactant has little effect in NaBr particles, NaCl and NaI covered particles experience appreciable shifts in their deliquescence relative humidities, with different trends observed for each of the acids studied. In efflorescence mode, the overall effect of the organic covering is to retard the loss of water in the particles. It has been observed that the presence of gaseous water in heterogeneously nucleated particles tends to displace the cover of hexanoic acid to energetically stabilize the system.

Analytical method development for the uptake study of different organic pollutants by crops cultivated in compost-amended soils

256 p.

Vanadyl arsenates as catalysts for selective oxidation of organic sulfides and alkenes

artículo científico (postprint)

Hydrothermal Synthesis and Study of Inorganic-Organic Hybrid Vanadate of Nickel(II) Coordination Complex with Pyrazine, Ni3(C4H4N2)3(V8O23)

Artículo científico: postprint