The interest in renewable natural resources, including plant oils, has become increasingly appealing due to the oil abundance, availability, and wide range of applications for polymers and polymeric materials thereof. In this dissertation, a library of plant oil-based acrylic monomers (POBMs) with a broad range of unsaturation was synthesized using a one-step transesterification. It is demonstrated that the unsaturation degree of plant oil remains preserved during the synthesis and determines the structure and properties of POBMs. The life cycle assessment (LCA) was conducted in this study to evaluate the environmental impact of soybean oil-based acrylic monomer (SBM) production. LCA was applied to provide guidance for SBM synthesis optimization, including the type of catalyst, the ratio between reactants, renewable sources (soybean oil/biodiesel), and solvent recycling. The performed LCA shows the positive effect of the inclusion of the solvent recycling step in the SBM synthesis. This study shows that POBMs behave as conventional vinyl monomers in free radical polymerization and copolymerization. The monomer unsaturation impacts polymerization rate and molecular weight of resulted polymers decreasing as follows: poly(OVM) > poly(SFM) > poly(SBM) > poly(LSM), due allylic termination presented during polymerization. A series of stable POBM-based latexes with high solid content (40-45 %) and monomer conversion (95-97 %) were synthesized using miniemulsion process. The incorporation of POBMs fragments provides the plasticizing effect on the resulting latex polymers, as seen by a noticeable decrease in their glass transition temperature (Tg). The crosslink density of POBM-based latex films follows the linear dependence vs. monomer feed unsaturation, providing a tool for controlling latex mechanical properties, including hardness, toughness, Young's modulus, etc. Besides, the presence of highly hydrophobic POBM fragments enhances water resistivity of latex coatings and films. Following the "greener" vector of research, a variety of stable latexes from high oleic soybean oil-based monomer (HOSBM) and cardanol, eugenol, and guaiacol derivatives were synthesized in miniemulsion. Resulting polymeric materials advantageously combine flexibility provided by HOSBM fragments with strength facilitated by aromatic biobased units.

Yes / In this perspective paper, we present challenges and opportunities that the chemical, biochemical and related industries pose to the process system engineering community to help deliver reliable and novel sustainable alternatives. More specifically, we highlight the need for a systems approach where model-based sustainable process synthesis, design, and analysis serve as opportunities to tackle the challenges. Three technology areas (interlinked to each other) that impact the sustainability of earth, namely, chemical processes linked with CO2 capture and utilization, biorefineries and water desalination are selected to highlight our views as well as the need for further development of computer-aided tools to efficiently solve the large and complex mathematical systems the problems represent. Analysis of these problems and their reported solutions indicate that opportunity exists for development of a new class of model-based methods and tools and their integration with the currently available ones to obtain the desired sustainability development goals.

The general objective has been to empirically analyze how Hotelling’s rule has predicted the crude oil price development over the last 100 years and if the rule can work as a framework to predict future resource prices. Hotelling’s rule has been perceived as both outdated and relevant, during the last decades. A general conclusion from previous research is that resource price-developments are more complex than Hotelling assumed. The analysis has been conducted through tests of variables like interest rates, time spans and extraction costs. The assumption of exponentially increasing resource prices has also been tested. The results obtained show no general support for the Hotelling-rule’s ability to predict future prices. Our results suggest that Hotelling’s rule predicts price paths best when a short time-span is considered. The lack of predictability is due to high volatility in resource prices, something Hotelling’s rule does not account for. / Det övergripande syftet med denna studie har varit att empiriskt analysera hur väl Hotellings-regel har förutspått utvecklingen av oljepriset under de senaste hundra åren och om regeln fungerar som ett bra ramverk för att kunna förutspå framtida resurspriser. Hotellings-regel har uppfattats som både föråldrad samt relevant under de senaste årtiondena. En generell slutsats från tidigare forskning är dock att utvecklingen av icke-förnybara resursers priser är mer komplex än vad Hotelling antog. Analysen har utförts genom tester av olika variabler som räntor, tidsperioder och utvinningskostnader. Antagandet om exponentiellt ökande resurspriser har också testats. De erhållna resultaten ger inget generellt stöd för Hotelling regeln som ett bra ramverk till att förutspå framtida resurspriser. Resultaten tyder dock på att Hotellings-regel förutspår framtida priser bäst när en kortare tidsperiod antas. Modellens avsaknad av förutsägbarhet är sannolikt på grund av volatilitet i resurspriser, något som Hotellings-regel inte tar fullt hänsyn till.

In order to reduce over-dependency on fossil fuels and to create an environment that is free of non-degradable plastics, and most importantly to reduce greenhouse gas emission, bio-based products are being developed from renewable resources through intense research to substitute conventional petrochemical-based plastics with renewable alternatives and to replace synthetic fibers with natural fibers. Many authors have done quite a lot of work on synthesizing polymers from renewable origin. Polylactic acid (PLA) has been developed and characterized, and it was found that it has enormous potential and can serve as an alternative to conventional thermoplastics in many applications. Modification of the plant oil triglycerides has been discussed by many authors, and research is still going on in this area. The challenge is how to make these renewable polymers more competitive in the market, and if possible to make them 100% bio-based. There is also a major disadvantage to using a bio-based polymer from plant oils because of the high viscosity, which makes impregnation of fibers difficult. Although natural fibers are hydrophilic in nature, the problem of compatibility with the hydrophobic matrix must be solved; however, the viscosity of the bio-based resin from plant oils will complicate the situation even more. This is why many authors have reported blending of the renewable thermoset resin with styrene. In the process of solving one problem, i.e reducing the viscosity of the renewable thermoset resin by blending with reactive diluents such as styrene, another problem which we intended to solve at the initial stage is invariably being created by using a volatile organic solvent like styrene. The solution to this cycle of problems is to synthesize a thermoset resin from plant oils which will have lower viscosity, and at the same time have higher levels of functionality. This will increase the crosslinking density, and they can be cured at room temperature or relatively low temperature. In view of the above considerations, the work included in this thesis has provided a reasonable solution to the compounded problems highlighted above. Three types of bio-based thermoset resins were synthesized and characterized using NMR, DSC, TGA, and FT-IR, and their processability was studied. The three resins were subsequently reinforced with natural fibers (woven and non-woven), glass fibers, and Lyocell fiber and the resulting natural fiber composites were characterized by mechanical, dynamic mechanical, impact, and SEM analyses. These composites can be used extensively in the automotive industry, particularly for the interior components, and also in the construction and furniture industries. Methacrylated soybean oil (MSO), methacrylic anhydride-modified soybean oil (MMSO), and acetic anhydride-modified soybean oil (AMSO) were found to be suitable for manufacture of composites because of their lower viscosity. The MMSO and MSO resins were found to be promising materials because composites manufactured by using them as a matrix showed very good mechanical properties. The MMSO resin can completely wet a fiber without the addition of styrene. It has the highest number of methacrylates per triglyceride and high crosslink density. / Akademisk avhandling för avläggande av teknologie doktorsexamen vid Chalmers Tekniska högskola försvaras vid offentlig disputation, den 6:e maj, Chalmers, KE-salen, Kemigården 4, Göteborg, kl. 10.00.

Le glycérol est valorisable par déshydratation en acroléine qui est un important intermédiaire chimique et peut être converti en une multitude de produits à valeur ajoutée dont l’acide acrylique qui est la base de nombreux polymères. Cette réaction est réalisée sur des catalyseurs acides comme les zéolithes protoniques qui donnent d’importants rendements initiaux en phase gazeuse (275-325°C) et à pression atmosphérique. Cependant, le principal inconvénient de ces matériaux est la désactivation rapide au cours du temps dû à la formation de dépôts carbonés appelés « coke ». L’ajout du fer sur les zéolithes H-BEA (larges pores) et H-MFI (pores moyens) a montré un effet fortement bénéfique sur cette réaction en présence d’air avec une formation supposée d’espèces actives qui permettraient de réduire de manière importante la désactivation du catalyseur et tout en favorisant la formation directe de l’acide acrylique sur la fonction métallique. Les zéolithes MFI au fer préparées par substitution isomorphe sont les plus performantes avec un rendement maximum en acide acrylique de 40% obtenu sur H-Fe3.8-Z-45 (préparé par synthèse hydrothermale). La zéolithe Np-Fe0.6-MFI-41 (préparé par traitement post-synthèse en milieu fluorure) permet d’obtenir un rendement en acroléine de plus de 80% après 24h de réaction, reproductible après régénération. Ce catalyseur est non seulement très actif, sélectif en acroléine, stable mais aussi régénérable, ce qui le place parmi les meilleurs pour ce procédé. / Glycerol is recoverable by dehydration into acrolein, which is an important chemical intermediate and can be converted into a variety of value-added products including acrylic acid that is the basis of many polymers. This reaction is carried out over acid catalysts, such as protonic zeolites which provide significant initial yields in the gas phase (275-325° C) and at atmospheric pressure. However, the main drawback of these materials is the rapid deactivation over time because of the formation of carbonaceous deposits known as "coke". The addition of iron over H-BEA (large pore) and H-MFI (mean pore) zeolites showed a highly beneficial effect on this reaction in the presence of air with an assumed formation of active species that would reduce significantly catalyst deactivation while promoting the direct formation of the acrylic acid on the metal function. H-MFI iron zeolites prepared by isomorphous substitution are the most efficient with a maximum acrylic acid yield of 40% obtained over H-Fe3.8-Z-45 (prepared by hydrothermal synthesis). Np-Fe0.6-MFI-41 zeolite (prepared by post-synthesis treatment in a fluoride medium) gives an acrolein yield of 80% after 24 hours of reaction, reproducible after regeneration. This catalyst is not only very active, selective to acrolein and stable but also regenerable, which places it among the best for this process.

This dissertation provides three models pertaining expropriation and production decisions in the natural resources industries. The first two chapters are intertwined: in these, the government relies on two tools to capture the rents from privately-owned Natural Resources Companies, a corporate income tax and the possibility of expropriating the assets. A real options model is used to assess the effect that progressiveness in taxation has on the political risk of a natural resources project. In the first chapter, we discover that under certain conditions for the underlying commodity: low prices or forward curves in backwardation - the introduction of an equivalent but more progressive tax regime decreases the political risk and the corresponding deadweight loss. However, when initial prices are too high or initial futures curves are in strong contango, the introduction of a progressive tax regime ends up significantly increasing the risks. In the second chapter, producers are able to foresee the risks of expropriation and thus change their behaviour: the results are mixed. As in the previous case, with lower prices and less tendency to expropriate, the scheduling of production allows for gains in the value of the operation for the firms. More progressive tax regimes end up being detrimental to the government, which in some cases can even result in a non-stable equilibrium with the producers and governments trying to outguess each other and end up cycling both the production and the expropriation probability in order to maximise their respective expected value for the operations. This has a detrimental effect for all parties involved. Finally, the third chapter introduces the possibility that a government levies royalties over sales. The development of home-based institutions is going to affect the amount of tax evasion that a government will face and thus determine the appropriate combination of taxes that it must choose. We find that when the host country's tax and technological capacity are too low, a state has no incentives to improve its institutions and becomes trapped in a low tax, low revenue situation: what we call a Royalty Trap. We end up by showing the evolution of tax capture in Chile during the 20th century to illustrate how these concepts might be applied.

Orientador: Prof. Dr. Sinclair Mallet Guy Guerra / Tese (doutorado) - Universidade Federal do ABC, Programa de Pós-Graduação em Energia, 2014. / A perspectiva de que o petróleo pode ser o caminho para levar o Brasil ao patamar de desenvolvimento tão sonhado pelos brasileiros pode estar próxima de acontecer. Sem sombra de dúvida, as novas reservas descobertas já colocam o Brasil em outro patamar no mapa geopolítico do petróleo. A camada pré-sal é uma faixa rochosa que se estende por aproximadamente 800 km entre os estados do Espírito Santo e Santa Catarina, a cerca de 300 km da costa, possui de seis a sete mil metros de profundidade e com petróleo e gás abaixo de la. A grandeza dessa descoberta pode colocar o Brasil no cenário nacional e internacional como grande produtor e possível exportador do óleo. Além disso, permitirá usá-lo como matéria-prima de seus inúmeros derivados e subprodutos. No tocante à renda a ser gerada com sua exploração as expectativas são imensas, mesmo com as constantes variações do preço internacional do petróleo. Considerando este um produto essencial e sem substituto próximo, seus elevados preços, assim como a demanda crescente, seria possível afirmar que países detentores de reservas teriam teoricamente enriquecimento rápido e contínuo. Porém, os fatos históricos têm apontado situações diferentes entre países que possuem reservas e exportam. A indústria brasileira do petróleo é bastante jovem comparada com o resto do mundo, mas nem por isso menos importante e eficiente. Com tantas possibilidades em vista, pesquisadores passaram a buscar respostas e traçar cenários do que poderá acontecer ao Brasil, na hipótese de o país se tornar um grande exportador de petróleo. Nesse sentido, nosso governo levou a pauta a um novo marco regulatório, que visa manter maior proteção do estado em relação ao Pré-Sal, haja vista que, desde os anos 90, quando foi aberto seu capital para o setor privado, a produção nacional ficou em parte no poder de grandes companhias que não têm por objetivo canalizar a renda do petróleo em prol da economia brasileira. Atualmente há muitas pesquisas que visam responder questionamentos advindos do Pré-Sal, como exemplo, quais serão os fatores econômicos determinantes e impactos dos mesmos com a exploração do Pré-Sal na economia brasileira? Em realidade não se coloca esse questionamento como um problema, mas sim a força das questões levantadas. A metodologia utilizada neste trabalho é composta por pesquisa bibliográfica e análise de dados com utilização de modelo dos recursos naturais não renováveis (RNNR) para otimizar variáveis que dão origem aos fatores de impulso para a economia brasileira. Os resultados obtidos apontam um preço estimado próximo do preço internacional do petróleo. Também os investimentos, poupança, capital humano e comércio externo serão fatores de impacto para o crescimento e desenvolvimento sócio-econômico do país. / A perspectiva de que o petróleo pode ser o caminho para levar o Brasil ao patamar de desenvolvimento tão sonhado pelos brasileiros pode estar próxima de acontecer. Sem sombra de dúvida, as novas reservas descobertas já colocam o Brasil em outro patamar no mapa geopolítico do petróleo. A camada pré-sal é uma faixa rochosa que se estende por aproximadamente 800 km entre os estados do Espírito Santo e Santa Catarina, a cerca de 300 km da costa, possui de seis a sete mil metros de profundidade e com petróleo e gás abaixo de la. A grandeza dessa descoberta pode colocar o Brasil no cenário nacional e internacional como grande produtor e possível exportador do óleo. Além disso, permitirá usá-lo como matéria-prima de seus inúmeros derivados e subprodutos. No tocante à renda a ser gerada The prospect that oil may be the way to lead Brazil to the level of development as dreamed by Brazilians can be close to happening. Without a doubt, the new reserves discovered already put Brazil on another level in the geopolitical map of the oil. The pre-salt layer is a rocky track that stretches for about 800 km between the states of Espírito Santo and Santa Catarina and is approximately 300 km from the coast. This layer has six to seven thousand feet deep and below it are oil and gas. The magnitude of this discovery could put Brazil in the national and international scene as a major producer and possible oil exporter. It will also use it as raw material for their derivatives and by-products. Regarding the income that is generated with its exploration expectations are immense, even with the constant changes in international oil prices. Whereas oil is an essential product and no close substitute, their high prices as well as increasing demand, it could be argued that countries holding reserves would theoretically rapid and continuous enrichment. However, the historical facts have shown different situations between countries that have reserves and export. The Brazilian oil industry is quite young compared to the rest of the world, but no less important and efficient. With so many possibilities to view, researchers began to look for answers and plot scenarios of what may happen to Brazil, should the country becoming a major oil exporter. In this sense, the Brazilian government took the agenda for a new regulatory framework, which aims to maintain greater state protection in relation to the pre-salt, given that, since the 90s, when it opened its capital to the private sector, production National was in power in part of large companies which does not aim to channel oil revenues in favor of the Brazilian economy. Currently there are many studies aimed at answering questions from the pre-salt, so they wonder what will be the economic determinants and impacts of these factors with the pre-salt exploration in the Brazilian economy? Actually this question does not arise as a problem, but the force of the issues raised. The methodology used in this study consists of literature search and data analysis with the use of model of exhaustible natural resources (RNNR) to optimize variables that give rise to boost factors for the Brazilian economy. The results show an estimated price near the international price of oil. Like, investments, savings, human capital and foreign trade will impact for growth and economic and social development factors.

Porous materials (e.g. zeolites, activated carbon, etc.) have found various applications in industry, such as the use as sorbents, catalyst supports and membranes for separation processes. Recently, much attention has been focused on synthesizing porous polymer materials. A vast amount of tailor-made polymeric systems with tunable properties has been investigated. Very often, however, the starting substances for these polymers are of petrochemical origin, and the processes are all in all not sustainable. Moreover, the new polymers have challenged existing characterizing methodologies. These have to be further developed to address the upcoming demands of the novel materials. Some standard techniques for the analysis of porous substances like nitrogen sorption at 77 K do not seem to be sufficient to answer all arising questions about the microstructure of such materials. In this thesis, microporous polymers from an abundant natural resource, betulin, will be presented. Betulin is a large-scale byproduct of the wood industry, and its content in birch bark can reach 30 wt.%. Based on its rigid structure, polymer networks with intrinsic microporosity could be synthesized and characterized. Apart from standard nitrogen and carbon dioxide sorption at 77 K and 273 K, respectively, gas sorption has been examined not only with various gases (hydrogen and argon) but also at various temperatures. Additional techniques such as X-ray scattering and xenon NMR have been utilized to enable insight into the microporous structure of the material. Starting from insoluble polymer networks with promising gas selectivities, soluble polyesters have been synthesized and processed to a cast film. Such materials are feasible for membrane applications in gas separation. Betulin as a starting compound for polyester synthesis has aided to prepare, and for the first time to thoroughly analyse a microporous polyester with respect to its pores and microstructure. It was established that nitrogen adsorption at 87 K can be a better method to solve the microstructure of the material. In addition to that, other betulin-based polymers such as polyurethanes and polyethylene glycol bioconjugates are presented. Altogether, it has been shown that as an abundant natural resource betulin is a suitable and cheap starting compound for some polymers with various potential applications. / Das Bestreben, ölbasierte Produkte durch nachwachsende Rohstoffe zu ersetzen, hat dazu geführt, dass in immer größerer Zahl günstige, reichlich vorhandene Naturstoffe als Ausgangsstoffe für chemische Synthesen untersucht werden. In dieser Arbeit werden Polymere auf Basis von Betulin, einem aus Birkenrinde extrahierten Naturstoff, vorgestellt. Betulin ist zu 30 Gewichtsprozent in Birkenrinde enthalten. Da Betulin ein Nebenprodukt der Holzindustrie ist, ist es kostengünstig und sein Einsatz als Ausgangsstoff äußerst lukrativ. Die ersten Berichte über Betulin-basierte Polymere sind in den 1980er Jahren in Russland und Finnland erschienen, in den Ländern mit großen natürlichen Vorkommen an Birken. Betulin wurde in dieser Arbeit verwendet, um sogenannte mikroporöse Polymere herzustellen. Dies sind Stoffe mit Poren von molekularer Dimension. Mikroporöse Materialien sind wegen ihrer potentiellen Anwendung als Katalysatorträger und Gasseparationsmembranen hochinteressant. Die Klasse mikroporöser Polymere wurde durch die Synthese von unlöslichen Betulin-basierten Polyesternetzwerken erweitert. Außerdem gelang es, lösliche Polyester in Form dünner Filme herzustellen. Diese zeigten vielversprechende Ergebnisse in der Trennung von Stickstoff und Kohlendioxid und weisen somit Potential für die Nutzung als Membran auf. Dies könnte z. B. für Kohlendioxid-Reduzierung in Postcombustion-Verfahren interessant sein. Überdies wurde gezeigt, dass Stickstoffadsorption bei 77 K nicht ohne weiteres als Standardmethode für die Analyse von mikroporösen Materialien geeignet ist und dass die mikroporösen Materialien ferner durch Stickstoffadsorption bei 87 K und andere Gassorptionsmethoden bei verschiedenen Temperaturen zu charakterisieren sind. Diese Arbeit trägt zum besseren Verständnis mikroporöser Polymere bei.

In the recent years, governments have encouraged the utilization of renewable energy by providing incentives to investors, and enhancing traditional practices in the sector. For example, in Ontario, Canada, local distribution companies can now legally own and operate up to 10 MW generating plant per location as long as it is from a renewable source. Although this trend results in some operational benefits for the host networks, it also creates specific technical challenges and economic problems. New modeling approaches are needed to account for the main features of power produced by these facilities, namely, the uncertainty and uncontrollability. The uncertainty of power produced by weather-based generating facilities affects the decisions of different activities related to the operation of distribution systems. Examples of these tasks include power procurement decisions, the assessment of voltage magnitude variation, and reactive power management. If not properly included, uncertainty could result in non optimal outcome of operational activities of a distribution system operator. Based on different optimization techniques, the thesis introduces several models that capture the uncertain behavior of renewable resources. Two operational tasks were selected for application using the enhanced models: economical operation of distribution system and impact assessment on voltage magnitude. The power procurement problem is an operational challenge to acquire the correct economic mix of power purchases to supply the demand of a local distribution company. Three models have been presented to formulate the power procurement problem with a consideration of the stochastic nature of renewable generation. These models select the optimal quantities of bilateral contracts under uncertain renewable generation and give the option to decision makers to recalculate the powers from other sources. In one of these proposed models, the mean-variance theory is utilized to evaluate the risk associated with the variation of renewable power output on the financial efficiency of a local distribution company. Unlike previous studies, in which renewable power production is identified as a decision variable, in this work the generation from these units is represented as a parameter to model their feature of uncontrollability. Comparison of results obtained from using the proposed models showed that the degree of uncertainty plays an important role in selecting the proper mix. In general, stochastic based algorithms are superior to deterministic approaches when increasing contributions from renewable resources are considered. A major technical problem that may be caused by the uncertain generation of renewable units is the increase of voltage variation. The second part of the thesis introduces a methodology based on a Monte-Carlo technique to assess new installation depending on its impact on the quality of supply voltage. Two different standard measures for supply voltage quality are applied in this approach to provide the decision maker a tool that can be used to authorize new connections of renewable generation. The consistency of results obtained by the two indices applied in the proposed methodology encourages adopting the proposed approach for evaluating the impact of new connections of renewable resources. The models proposed in the thesis contribute to promote safer integration of renewable resources in distribution systems by modeling two main features: uncertainty and non-controllability.

Die Anlage von Kurzumtriebsplantagen (KUP) mit schnellwachsenden Baumarten auf landwirtschaftlichen Flächen kann sowohl Synergien freisetzen als auch negative Auswirkungen für Naturschutzziele haben. Entscheidend dafür sind die Flächenauswahl sowie die konkrete Gestaltung der KUP-Anlage und ihre Bewirtschaftung. Die Broschüre widmet sich insbesondere dem Aspekt Flächenauswahl. Dazu wird eine weiterentwickelte Methode zur fachlichen Einschätzung der Eignung von Ackerflächen für Kurzumtriebsplantagen im Einklang mit dem Naturschutz vorgestellt. Anhand von 93 Einzelkriterien aus den Komplexen »Flächennaturschutz« und »Artenschutz« wurde ein Bewertungsalgorithmus entwickelt und am Praxisbeispiel des Landkreises Görlitz in Ostsachsen getestet. Im Ergebnis einer GIS-Analyse wurde für die Ackerflächen dieses Landkreises eine abgestufte, naturschutzfachlich begründete Synergieklassen-Kulisse als fachliche Empfehlung für eine gezielte Flächenauswahl für KUP gebildet.