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Biobased Thermosets from Vegetable Oils. Synthesis, Characterization, and PropertiesGerard Lligadas PuigEl desenvolupament sostenible va esdevenir com una de les idees claus del segle 20. S'entén per desenvolupament sostenible aquell tipus de desenvolupament que és capaç de satisfer les necessitats actuals sense comprometre els recursos i possibilitats de les futures generacions. Per assolir un desenvolupament sostenible és necessari promoure un desenvolupament social i econòmic pendent en tot moment del medi ambient. La conservació i la gestió dels residus és especialment important en aquest procés. La creixent demanda de productes derivats del petroli, juntament amb la disminució progressiva de les reserves de petroli són algunes de les moltes raons que han encoratjat la industria química a començar a utilitzar les fonts renovables com a matèria prima.En aquest context, en els darrers anys l'atenció s'ha centrat en la utilització de recursos anualment renovables, com són els recursos agrícoles, en la producció d'una gran varietat de productes industrials. Un dels recursos renovables més interessants per a la indústria química són els olis vegetals degut a la seva elevada disponibilitat i el seu ampli ventall d'aplicacions. Els olis vegetals formen part de la família de compostos químics coneguts com lípids, i estan constituïts majoritàriament per molècules de triglicèrids. Els triglicèrids estan formats per tres molècules d'àcid gras unides a una molècula de glicerol mitjançant enllaços ester. Els àcids grassos que es troben en la majoria d'olis vegetals estan constituïts per cadenes alifàtiques insaturades de entre 14 i 22 àtoms de carboni.La explotació industrial dels recursos naturals està actualment en el punt de mira de la comunitat científica. Concretament, el desenvolupament de materials polimèrics derivats de fonts renovables està rebent un interès creixent degut a la incertesa en el preu i les reserves de petroli. La substitució del petroli per productes derivats de fonts renovables és consistent amb el concepte de desenvolupament sostenible. El propòsit del treball portat a terme en aquesta tesi doctoral va ser desenvolupar nous materials termoestables utilitzant olis vegetals com a productes de partida. En el capítol 1 es discuteix la contribució de la química en el desenvolupament sostenible i es descriuen les possibilitats dels olis vegetals com a productes de partida en la síntesi de materials polimèrics. El capítol 2 descriu la preparació de dos noves famílies de materials híbrids orgànics-inorgànics derivats d'olis vegetals. Es descriu síntesi i caracterització de polímers híbrids derivats d'àcids grassos que contenen dobles enllaços carboni-carboni terminals utilitzant la reacció d'hidrosililació com a reacció d'entrecreuament, i la preparació de polímers derivats d'oli de llinosa epoxidat nanoreforçats amb silsesquioxans polièdrics. En el capítol 3 es descriu la síntesi d'un nou compost fosforat derivat de fonts renovables. Aquest compost s'ha utilitzat com a compost retardant a la flama reactiu en la preparació de resines epoxi derivades de fonts renovables amb propietats de resistència a la flama. La incorporació de fòsfor en resines epoxi d'aquest tipus ha donat lloc a polímers amb bones propietats de resistència a la flama. Finalment, en el capítol 4 es descriu la preparació d'una nova família de polièter poliols derivats d'oleat de metil epoxidat com a font renovable. Aquests poliols s'han utilitzat en la síntesi de poliuretans amb aplicacions específiques: poliuretans que incorporen silici amb propietats de resistència a la flama, i poliuretans segmentats amb aplicacions en biomedicina.Biobased Thermosets from Vegetable Oils. Synthesis, Characterization, and PropertiesGerard Lligadas PuigSustainable development, which became a key idea during the 20th century, may be regarded as the progressive and balanced achievement of sustained economic development, and improved social equity and environmental quality. Sustainable development comprises the three components of society, environment, and economy, and its goals can only be achieved if all three components can be satisfied simultaneously.The conservation and management of resources is especially important to this process. The growing demand for petroleum-based products and the resulting negative impact on the environment, plus the scarcity of non-renewable resources, are some of the many factors that have encouraged the chemical industry to begin using renewable resources as raw materials.This situation has led to considerable attention being focused recently on the use of annually renewable agricultural feedstock to produce a wide range of base chemicals and other industrial products. The renewable raw materials that are most important to the chemical industry are natural oils and fats because of their high availability and versatile applications. Vegetable oils constitute about 80% of the global oil and fat production, with 20% (and declining) being of animal origin. The use of these materials offers an alternative approach that is both sustainable and, with the right application, far more environmentally benign than fossil sources.Vegetable oils and fats form part of a large family of chemical compounds known as lipids. Vegetable oils are predominantly made up of triglyceride molecules, which have the three-armed star structure. Triglycerides comprise of three fatty acids joined at a glycerol junction. Most of the common oils contain fatty acids that vary from 14 to 22 carbons in length, with 0 to 3 double bonds per fatty acid.Research into the industrial exploitation of products derived from renewable resources is currently of immense international importance. In particular, the development of polymer materials from renewable resources is receiving considerable attention since the availability of crude oil will become severely restricted within the foreseeable future. The replacement of crude oil by renewable raw materials is also consistent with the aim of global sustainability.The purpose of the study reported in this thesis was to develop new biobased thermosetting polymers from vegetable oils as renewable resources. To achieve this goal, the experimental work focused on exploiting the reactivity of unsaturated fatty compounds. Chapter 1 discusses the contribution of chemistry to sustainable development, and also presents an overview of recent developments in the chemistry of vegetable oil-based polymers. Chapter 2 describes the preparation of two new types of organic-inorganic hybrid materials from vegetable oils. Hybrids with promising properties for optical applications were prepared by the hydrosilylation of alkenyl-terminated fatty acid derivatives with several hydrosilylating agents, and the first example of the preparation of biobased polyhedral oligomeric silsesquioxanes-nanocomposites from vegetable oil derivatives is reported. Chapter 3 describes the synthesis of a new phosphorus-containing fatty acid derivative. This compound is used as a reactive flame-retardant in the preparation of flame-retardant epoxy resins from terminal epoxy fatty acid derivatives. The incorporation of phosphorous into biobased epoxy resins yields polymers with good flame-retardant properties. Finally, chapter 4 describes the preparation of a new family of epoxidized methyl oleate based polyether polyols. These polyols are used in the synthesis of polyurethanes, some with specific applications: silicon-containing polyurethanes with enhanced flame-retardant properties, and polyurethane networks with potential applications in biomedicine.

The oil and gas well completion method of hydraulic fracturing faces several environmental challenges: the process is highly water-intensive; it generates a significant volume of wastewater; and it is associated with widespread flaring of co-produced natural gas. One possible solution to simultaneously mitigate these challenges is to use the energy from flared natural gas to power on-site wastewater treatment, thereby reducing 1) flared gas without application, 2) the volumes of wastewater, and 3) the volumes of freshwater that need to be procured for subsequent shale production, as the treated wastewater could be reused. In regions with minimal flaring a potential solution is to couple renewable electricity (generated from solar and wind energy) with on-site wastewater treatment, thereby 1) reducing the volumes of wastewater, 2) reducing the volumes of freshwater that need to be procured for subsequent shale production, and 3) displacing fossil fuel energy for treatment. This study builds an analytical framework for assessing the technical potential of these approaches. In this research, the hydraulic fracturing wastewater characteristics (such as quality, quantity, and flow rates) were considered along with various treatment technologies best suited to utilizing natural gas and renewable electricity, using the Permian Basin in west Texas as a geographic test bed for analysis. For the analysis looking at using flared natural gas energy for on-site treatment, the required volume of gas to meet the thermal energy requirements for treatment was calculated on a per-well basis. Additionally, the volume of product water (defined here as the treated water that can be reused) based on the technology type was determined. Finally, the theoretical maximum volume of product water that could be generated using the total volume of natural gas that was flared in Texas in 2012 as a benchmark was calculated. It was concluded that the thermal energy required to treat wastewater that returns to the surface over the first ten days after a well is completed is 140–820 Million British Thermal Units (MMBTU) and would generate 750–6,800 cubic meters of product water depending on the treatment technology. Additionally, based on the thermal technologies assessed in this study, the theoretical maximum volume of product water that can be generated statewide using the energy from the flared gas in 2012 is 180–540 million cubic meters, representing approximately 3–9% of the state’s annual water demand for municipal purposes or 1–2.4% of total statewide water demand for all purposes. This is enough gas to treat more water than was projected would be used for the entire mining sector in 2010 in Texas. For the analysis coupling renewable electricity with on-site treatment, the necessary energy for water management upstream and downstream of a well site was calculated and compared with the current energy requirements and those of a proposed strategy where a portion of the wastewater is treated on-site and reused on a subsequent well. Through this analysis, it was determined that implementing on-site treatment using renewable electricity could reduce freshwater requirements by 11–26%. Finally, it was calculated that this approach could displace approximately 16% of the fossil fuel energy requirements for pumping freshwater, trucking that water to the well site, and trucking wastewater to a disposal well. / text

The thesis deals with renewable resources, their history, development and support with special emphases on photovoltaics. The thesis turns to particular selected states, where the level and forms of support of renewables are analysed, again with emphases on photovoltaics. The thesis contains a chapter dealing with the support of photovoltaics in the Czech Republic, to which refers the applied part of the thesis -- the build-up of photovoltaic power plant in the Czech Republic in year 2008 in comparison with the one realised in 2010 from the cost-profit point of view.

With power system restructuring, continuous growth of demand, and deregulation, small, scattered generators referred to as Distributed Generation (DG) are predicted to play a key role in the power distribution system. Moreover, among the different types of DG units, it is widely accepted that renewable DG units are the key to a sustainable energy supply infrastructure, since they are both inexhaustible and non-polluting. However the intermittent nature and the uncertainties associated with the renewable resources create special technical and economical challenges that have to be comprehensively investigated in order to facilitate the deployment of these DG units in the distribution system. The objective of the work proposed in this thesis is to tackle some of the challenges associated with the increased penetration of renewable DG units into existing distribution systems. This includes the study of the impact of different renewable DG units on the supply adequacy of the distribution system, and the development of planning technique that optimally allocate renewable DG units into the distribution system. Furthermore, a methodology is proposed to check the feasibility of implementing energy storage system (ESS) into the distribution system to mitigate the problems associated with the high penetration of renewable DG units. These problems include the maximum reverse power flow limit, the equipment rating limit, and the voltage limit on each bus. The first step toward the accomplishment of this work is to model the random behaviour of the renewable resources (i.e. wind speed and solar irradiance). Here, different approaches are proposed to model the random behaviour of both wind speed and solar irradiance, either chronologically or probabilistically. Among those approaches are a novel technique of annual wind speed estimation based on a constrained Grey predictor, and a new implementation of the probability density function (pdf) of the clearness index so as to model solar irradiance using Monte Carlo Simulation (MCS). Supply adequacy of distribution systems is assessed based on well-being criteria during different modes of operation (i.e. grid-connected mode and islanding mode), using analytical and (MCS) techniques. During the grid-connected mode, from the load perspective, the substation transformers act as generating units. Therefore, supply adequacy of distribution systems is assessed by considering that the generating units of the distribution system are the substation transformers and the DG units. During the islanding mode of operation, the island is acting as a small autonomous power system (SAPS) and the most important issue during this mode of operation is to determine the probability of the island to be successful (the DG power output within the island matches the load) or a failure (there is a deficit in power generation). The focus of the model developed to optimally allocate the renewable DG units in existing distribution systems is to minimize annual energy losses and at the same time, avoid any violation of the system constraints under any operating condition. The methodology is based on generating a probabilistic generation-load model that combines all possible operating conditions of the renewable DG units with their probabilities, hence accommodating this model in a deterministic planning problem. The objective function of the planning formulation is to minimize annual energy losses; whereas the constraints include the voltage limits, the feeders’ capacity, the maximum penetration limit, and the discrete size of the available DG units. The objective of the methodology proposed for allocating an ESS into distribution systems with high penetration (greater than 20% of the feeder capacity) of renewable energy is to maximize the benefits for both the DG owner and the utility. This is done by sizing the ESS to accommodate the entire surplus of renewable energy, and then allocating it within the system in order to minimize the annual cost of the electricity.

With power system restructuring, continuous growth of demand, and deregulation, small, scattered generators referred to as Distributed Generation (DG) are predicted to play a key role in the power distribution system. Moreover, among the different types of DG units, it is widely accepted that renewable DG units are the key to a sustainable energy supply infrastructure, since they are both inexhaustible and non-polluting. However the intermittent nature and the uncertainties associated with the renewable resources create special technical and economical challenges that have to be comprehensively investigated in order to facilitate the deployment of these DG units in the distribution system. The objective of the work proposed in this thesis is to tackle some of the challenges associated with the increased penetration of renewable DG units into existing distribution systems. This includes the study of the impact of different renewable DG units on the supply adequacy of the distribution system, and the development of planning technique that optimally allocate renewable DG units into the distribution system. Furthermore, a methodology is proposed to check the feasibility of implementing energy storage system (ESS) into the distribution system to mitigate the problems associated with the high penetration of renewable DG units. These problems include the maximum reverse power flow limit, the equipment rating limit, and the voltage limit on each bus. The first step toward the accomplishment of this work is to model the random behaviour of the renewable resources (i.e. wind speed and solar irradiance). Here, different approaches are proposed to model the random behaviour of both wind speed and solar irradiance, either chronologically or probabilistically. Among those approaches are a novel technique of annual wind speed estimation based on a constrained Grey predictor, and a new implementation of the probability density function (pdf) of the clearness index so as to model solar irradiance using Monte Carlo Simulation (MCS). Supply adequacy of distribution systems is assessed based on well-being criteria during different modes of operation (i.e. grid-connected mode and islanding mode), using analytical and (MCS) techniques. During the grid-connected mode, from the load perspective, the substation transformers act as generating units. Therefore, supply adequacy of distribution systems is assessed by considering that the generating units of the distribution system are the substation transformers and the DG units. During the islanding mode of operation, the island is acting as a small autonomous power system (SAPS) and the most important issue during this mode of operation is to determine the probability of the island to be successful (the DG power output within the island matches the load) or a failure (there is a deficit in power generation). The focus of the model developed to optimally allocate the renewable DG units in existing distribution systems is to minimize annual energy losses and at the same time, avoid any violation of the system constraints under any operating condition. The methodology is based on generating a probabilistic generation-load model that combines all possible operating conditions of the renewable DG units with their probabilities, hence accommodating this model in a deterministic planning problem. The objective function of the planning formulation is to minimize annual energy losses; whereas the constraints include the voltage limits, the feeders’ capacity, the maximum penetration limit, and the discrete size of the available DG units. The objective of the methodology proposed for allocating an ESS into distribution systems with high penetration (greater than 20% of the feeder capacity) of renewable energy is to maximize the benefits for both the DG owner and the utility. This is done by sizing the ESS to accommodate the entire surplus of renewable energy, and then allocating it within the system in order to minimize the annual cost of the electricity.

Introducción y antecedentes El concepto de desarrollo sostenible surgió como idea principal tras la reunión de la comisión Brundtland en 1987. Esta reunión fue organizada por Naciones Unidas con el fin de tratar el deterioro del medio ambiente, originado por el desarrollo descontrolado de la humanidad. El desarrollo sostenible fue definido como un avance social y económico que asegure una vida sana y productiva al ser humano, pero que no comprometa las posibilidades de desarrollo de las generaciones venideras. Entre las conclusiones alcanzadas, se resaltó la necesitad de disponer de una mayor variedad de fuentes de energía. La filosofía de esta cumbre fue recogida en Agenda 21, un documento que pretendía servir como guía general de actuación para alcanzar un desarrollo sostenible a todos los niveles. Respecto a las ciencias, Agenda 21 subrayaba la necesidad de emplear todo el conocimiento científico en la consecución de los objetivos del desarrollo sostenible. En este sentido, la Environmental Protection Agency acuñó en 1998 un término, Green Chemistry, que reunía estas ideas y las aplicaba a la química a través de 12 principios que debían ser cumplidos en el camino hacia una química sostenible. Entre estos principios, el uso de fuentes renovables para la obtención de materias primas ha adquirido gran relevancia debido a las previsiones de agotamiento de una de las fuentes de energía y materias primas más importantes: el petróleo. Los aceites vegetales se incluyen entre estas fuentes renovables de materias primas, siendo actualmente una de las fuentes renovables más utilizadas por la industria química. Los aceites vegetales están básicamente compuestos por triglicéridos, que son moléculas formadas por glicerol y tres ácidos grasos. En general los ácidos grasos pueden ser completamente saturados o contener varios dobles enlaces que en algunos casos pueden encontrarse conjugados, pero también existen ácidos grasos que contienen grupos hidroxilo o epóxido. Cada aceite vegetal posee una distribución característica de ácidos grasos que determina sus propiedades físicas y químicas. En lo que respecta a la química de los polímeros, los aceites vegetales constituyen una atractiva materia prima debido a la amplia gama de transformaciones químicas que pueden llevarse a cabo para sintetizar monómeros de diversa naturaleza. La epoxidación de los dobles enlaces internos es la transformación más común, ya que permite, a través de la apertura del anillo oxiránico con diferentes reactivos, la introducción de una gran variedad de grupos funcionales. Los dobles enlaces internos pueden polimerizarse directamente en condiciones térmicas, con iniciadores de radicales o por polimerización catiónica. / Introducction The sustainable development concept came out of the United Nations Commision on Environment and Development in 1987 (Bruntland Commission) and it is defined as "the development that meets the needs of the present without compromising the ability of future generations to meet their own needs". From this point, both the society and the industry have considered what a sustainable development really means and the best ways to start to achieve it from their own standpoints. The principles of the United Nations Conference on environment and Development (UNCED) held in June 1992 in Rio de Janeiro, and Agenda 21, were formulated with the aim of preparing the world for the challenges of the 21st century. In this context, during the early 1990s the US Environmental Protection Agency (EPA) coined the phrase Green Chemistry "To promote innovative chemical technologies that reduce or eliminate the use of generation of hazardous substances in the design, manufacture and use of chemical products". The main challenges of Green Chemistry and Engineeiring can be summarized as: · utilizing renewable instead of scarce resources. · avoiding toxic/dangerous chemicals in safer processes to obtain safer products. · minimizing energy use. · minimizing waste and resource use, re-using products, recovering and recycling materials. So making processes globally more efficient. Plant oils are one of the most widely applied renewable raw materials in the chemical industry for non-fuel applications. Vegetable oils are triglycerides (tri-esters of glycerol with long-chain fatty acids) with varying composition of fatty acids depending on the plant they are extracted from. Depending on the composition of plant oils, their Chemicals and physical properties are different.Vegetable oils are very used in polymer chemistry. Triglycerides have different reactive points through which we can obtain polymers from plant oils.There are two main approaches:The first one is the chemical modification of the triglycerides obtaining a large number of polymerizable monomers like expoxides or alcohols. The second approach is the direct polymerization of the carbon-carbon doubles bonds of plant oils through a free radical or a cationic mechanism.The free radical polymerization of double bonds has received less attention than cationic mechanism which has been very studied by Larock's group.In both cases thermosetting polymers with comparable properties to those of industrial can be obtained. Because of increasing use of synthetic polymeric materials during the lasts decades and the large fraction of the fire load in homes, it is necessary the use of fire retardants to reduce combustibility of the polymers, and smoke or toxic fume production. To get these requirements, the development of effective flame retardant materials is a key factor. To reduce the flammability, flame retardants can act in the gas phase or in condensed phase. In the gas phase fire retardants act as scavengers of the highly reactive radical species that propagate the combustion. In the condensed-phase fire retardants interfere in the thermal degradation processes modifying the reaction pathways and promoting the formation of char instead of volatile degradation products. Finally some flame retardants can act in both phases. Objectives The main objective of this Thesis was to develop new fire retardant biobased thermosets from vegetable oils as renewable resources. To achieve this goal it was carried out the cationic copolymerization of soybean oil, styrene and divinylbenzene with different silicon-or boron-or phosphorus containing comonomers.

In der Broschüre werden Anbau, Umweltwirkungen und Verwertungsmöglichkeiten des Miscanthus erläutert. Miscanthus, auch Chinaschilf genannt, ist eine sehr massenwüchsige Pflanze, die zur Familie der Süßgräser gehört. Die Pflanze ist ein bedeutender Rohstoff für die stoffliche und energetische Verwertung. Unter den Standortbedingungen Sachsens gedeiht Miscanthus gut und liefert wirtschaftliche Erträge. Die Broschüre richtet sich an Landwirte als Rohstoffproduzenten, aber auch an Nutzer und Verarbeiter des nachwachsenden Rohstoffs.

Auf arsen- und schwermetallbelasteten Böden im Raum Freiberg/Sachsen erfolgten Kalkdüngungsversuche und der Anbau von Weiden und Pappeln zur energetischen Verwertung. Nach der Kalkung auf Acker- und Grünlandflächen nahm der pflanzenverfügbare Anteil an Cadmium und Blei im Oberboden ab, nicht jedoch bei Arsen. Obwohl der Boden des Grünlandes hoch mit Blei und Arsen belastet war, wurde der Futtermittelgrenzwert nur vereinzelt bei Arsen und teilweise bei Cadmium überschritten. Bei Cadmium wurden erst mit zunehmendem pH-Wert und damit sinkendem pflanzenverfügbaren Anteil an Cadmium die Grenzwerte eingehalten. Die Kurzumtriebsplantage mit Pappeln und Weiden erreichte sehr gute Erträge. Sie lagen nach drei Anbaujahren bei 6,3 t TM/ha*a und nach weiteren zwei Jahren bei 16 t TM/ha*a. Weiden nahmen im Vergleich zu Pappeln die dreifache Menge an Cadmium und Zink auf. Die Einlagerung erfolgt insbesondere in den Blättern. Die belasteten Brennstoffe wurden in Feuerungsanlagen energetisch verwertet, die Aschen analysiert. Die Vergasung von Miscanthuspellets in einer zirkulierenden Wirbelschicht erfolgte problemlos.

Entlang eines offenen Ackerschlages wurde im Lehr- und Versuchsgut Köllitsch bei Torgau (Sachsen) zu Demonstrationszwecken ein Feldstreifen aus Pappeln, Weiden und Schwarzerlen angelegt. Untersucht wurden Bestandsentwicklung, Wirtschaftlichkeit und die ökologische Wirkung. Um die positiven Effekte des Feldstreifens auf das Landschaftsbild, den Winderosionsschutz und auf die Biodiversität aufrechtzuerhalten, wurden nach drei Vegetationsjahren nur zwei von insgesamt vier Reihen geerntet. Die höchsten Erträge der insgesamt sieben Pappelsorten zeigten die Pappelsorten »Max 4«, »Max 3« und »Max 1« (je ca. 9 t TM/ha*a), gefolgt von der Sorte »Androscoggin«. Deutlich schwächer schnitt die Weidensorte »Gigantea« ab. Der Anbau der Pappelsorte »Beaupré« ist wegen der Anfälligkeit für Pappelrost nicht zu empfehlen. Bei der Weide wird bei vollmechanisierter Ernte mit Feldhäcksler, 21 Jahren Standzeit und dreijährigem Umtrieb bei 12.000 Pflanzen je Hektar und einem Ertrag von 10 t TM/ha*a ein Erlös von 478 Euro/ha*a (133 Euro ohne Zahlungsansprüche) erzielt. Das Ergebnis verbessert sich bei geringerer Pflanzdichte, dreijährigem Umtrieb oder höherem Ertrag. Das Ergebnis bei Anbau von Pappel liegt bei gleichen Annahmen auf Grund der höheren Pflanzgutkosten unter dem von Weide. Der Anbau ist eine wirtschaftlich sinnvolle Ergänzung zu den etablierten einjährigen landwirtschaftlichen Kulturen. Floristische und faunistische Erhebungen belegen, dass die Feldstreifen einen Lebensraum für diverse Pflanzen der Ruderal- und Ackerflora sowie gefährdete Spinnen und Laufkäfer bietet. Der ökologische Wert eines Feldstreifens liegt über dem einjähriger Feldkulturen, aber erreicht nicht den einer Naturschutzhecke.