abstract: One of the greatest problems facing society today is the development of a sustainable, carbon neutral energy source to curb the reliance on fossil fuel combustion as the primary source of energy. To overcome this challenge, research efforts have turned to biology for inspiration, as nature is adept at inter-converting low molecular weight precursors into complex molecules. A number of inorganic catalysts have been reported that mimic the active sites of energy-relevant enzymes such as hydrogenases and carbon monoxide dehydrogenase. However, these inorganic models fail to achieve the high activity of the enzymes, which function in aqueous systems, as they lack the critical secondary-shell interactions that enable the active site of enzymes to outperform their organometallic counterparts. To address these challenges, my work utilizes bio-hybrid systems in which artificial proteins are used to modulate the properties of organometallic catalysts. This approach couples the diversity of organometallic function with the robust nature of protein biochemistry, aiming to utilize the protein scaffold to not only enhance rates of reaction, but also to control catalytic cycles and reaction outcomes. To this end, I have used chemical biology techniques to modify natural protein structures and augment the H2 producing ability of a cobalt-catalyst by a factor of five through simple mutagenesis. Concurrently I have designed and characterized a de novo peptide that incorporates various iron sulfur clusters at discrete distances from one another, facilitating electron transfer between the two. Finally, using computational methodologies I have engineered proteins to alter the specificity of a CO2 reduction reaction. The proteins systems developed herein allow for study of protein secondary-shell interactions during catalysis, and enable structure-function relationships to be built. The complete system will be interfaced with a solar fuel cell, accepting electrons from a photosensitized dye and storing energy in chemical bonds, such as H2 or methanol. / Dissertation/Thesis / Doctoral Dissertation Biochemistry 2016

Computational fluid dynamics (CFD) modeling and analysis were used in three projects: solar CO2 conversion modeling, improved coal combustion modeling using STAR-CD, and premixed combustion modeling. Each project is described below. The solar CO2 conversion modeling project involved CFD simulations of a prototype solar CO2 converter that uses sunlight to dissociate CO2 into CO and O2. Modeling was used to predict the performance of this prototype converter using three CFD software packages, and involved predicting the flow, heat transfer, and chemical kinetics. Accuracy was determined by comparison of model predictions and experimental data. Parametric modeling studies were performed in order to better understand converter performance and limitations. Modeling analysis led to proposed operational and design changes meant to improve converter performance. Modeling was performed to quantify the effects of proposed design modifications and operational adjustments. Modeling was also used to study the effects of pressure, some geometric design changes, and changing from pure CO2 to a CO2/He mixture. The insights gained from these modeling studies have played a key role in improving the performance of this process. The second project involved the implementation of advanced coal models into STAR-CD, a commercial CFD program. These coal models were originally developed for PCGC-3, a code developed at Brigham Young University. This project involved modifying modern PCGC-3 coal combustion and gasification models so that they could be incorporated into STAR-CD. Models implemented included a coal set-up subroutine, and coal reactions models for devolatilization, char oxidation, and vaporization. Each implemented model was tested to verify its accuracy by comparison of model predictions with experimental data. All implemented coal submodels were validated by comparison between overall modeling predictions and experimental data. These implemented coal models increased the capability of STAR-CD to model coal combustion and gasification systems. The third project was to assemble previously obtained experimental data on lean, premixed natural gas combustion. Velocity, temperature, and species concentration measurements were previously taken throughout a laboratory-scale gas turbine combustor using advanced laser diagnostics. However, these data were taken by different investigators at BYU over the course of 10 years, and the data were scattered through several publications, theses, and dissertations. This third project was to compile these data into a central location for analysis and distribution. This data set is excellent for validation of any comprehensive combustion model, and is now accessible to the public.

<p>Thermal, non-catalytic conversion of light olefins (C2= - C4=) was originally utilized in the production of motor fuels at several U.S. refineries in the 1920-30’s. However, the resulting fuels had relatively low-octane number and required harsh operating conditions (T > 450 oC, P > 50 bar), ultimately leading to its succession by solid acid catalytic processes. Despite the early utilization of the thermal reaction, relatively little is known about the reaction products, kinetics, and initiation pathway under liquid-producing conditions. </p> <p>In this thesis, thermal ethylene conversion was investigated near the industrial operating conditions, i.e, at temperatures between 320 and 500 oC and ethylene pressures from 1.5 to 43.5 bar. Non-oligomer products such as propylene and/or higher odd carbon products were observed at all reaction temperatures, pressures, and reaction extents. Methane and ethane were minor products (< 1 % each), even at ethylene conversions as high as 74 %. The isomer distributions revealed a preference for linear, terminal C4 and C5. The reaction order was found to be 2nd order with a temperature dependent activation energy ranging from 165 to 244 kJ/mol. The importance of diradical species in generating free radicals during a two-phase initiation process was proposed. The reaction chemistry for ethylene, which has only strong, vinyl C-H bonds starkly contrasted propylene, which possesses weaker allylic C-H bonds and showed preference for dimeric C6 products over C2-C8 non-oligomers. </p> <p>Extending this work further, the thermal oligomerization of ethylene was enhanced using high surface area supports such as silica and alumina. Both supports resulted in order of magnitude rate increases compared to the gas phase reaction, however the ethylene conversion rate with alumina was superior to silica by a factor of between 100 and 1,000. Additionally, the alumina evidently confers a catalytic function, resulting in altered product distributions, notably an increase in branched products such as isobutene and isopentenes. The oligomerization chemistry with alumina appears to reflect the involvement of Lewis acid sites rather than traditional Brønsted acid or transition metal catalysis, which operate via carbenium ion and metal-alkyl intermediates, respectively. </p>

O setor de transporte é um exemplo de atividade econômica que depende fundamentalmente das cadeias produtivas do petróleo, gás natural e biocombustíveis para sua operação, além de ser um dos principais consumidores da energia primária do país. Portanto, qualquer melhoria nos processos de produção e uso final dos combustíveis veiculares, repercute favoravelmente tanto na utilização dos recursos energéticos e o desempenho do setor, quanto no impacto ambiental e na economia nacional. Nesse sentido, faz-se necessário o desenvolvimento de uma metodologia que permita avaliar as diferentes rotas de produção e uso final, para determinar as principais fontes de degradação da energia e quantificar o impacto ambiental por meio de uma ferramenta apropriada. Uma valiosa ferramenta é a análise exergética ampliada, a qual provê uma oportunidade de quantificar os requerimentos exergéticos totais e não renováveis e as eficiências globais e, desse modo, perseguir e priorizar o uso daquelas fontes de energia mais favoráveis e amigáveis com o meio ambiente. A exergoeconomia, que visa à distribuição racional dos custos exergéticos entre os diversos produtos de uma mesma planta, usa a quantidade de exergia de cada produto como base para a distribuição da exergia despendida no respectivo processo. Desta forma, neste trabalho se apresenta uma análise comparativa sobre as rotas de produção e uso final dos combustíveis derivados do petróleo e o gás natural (inclusive o hidrogênio produzido da reforma a vapor), etanol, biodiesel, além da análise da geração e distribuição da eletricidade na matriz elétrica brasileira. Propõe-se o uso dos custos exergéticos unitários renováveis e não renováveis e as emissões de CO2 como indicadores para avaliar a intensidade exergética renovável e não renovável, o impacto ambiental e o desempenho termodinâmico no uso final. Este procedimento permite hierarquizar os diferentes processos de conversão de energia na produção e uso final de combustíveis veiculares, a fim de determinar as melhores opções para o setor de transporte. / Transportation sector is an example of economic activity that fundamentally depends on the supply chains of oil, natural gas and biofuels for its operation, as well as being a major consumer of primary energy in the country. Therefore, any improvement that could be achieved in the vehicle fuels production and end use processes, favorably affects both the use of energy resources and industry performance, as well as the environmental impact and the national economy. Accordingly, it is necessary to develop a methodology based on a suitable tool to evaluate the different routes of fuel production and end use, so that the main sources of energy degradation and the environmental impact can be determined and quantified. A valuable tool that serves that purpose is the extended exergy analysis, which provides an opportunity to quantify the total and non-renewable exergy requirements and overall efficiencies, and thereby pursue and prioritize the use of the most environmentally friendly sources of energy. Exergoeconomy, which attempts to rationally distribute the exergy cost among the several products of a single plant, uses the amount of exergy of each product as the basis for the distribution of exergy expended in the respective process. Thus, this work presents a comparative analysis of the production routes and end use of vehicles fuels derived from petroleum and natural gas (including hydrogen produced from methane steam reforming), ethanol, biodiesel, besides of the analysis of generation and distribution of electricity in the Brazilian electricity mix. Moreover, the renewable and non-renewable unit exergy costs and CO2 emissions are proposed as indicators, able to assess the renewable and non-renewable specific exergy consumption, the environmental impact and the thermodynamic performance of transportation sector. This procedure allows to hierarchize the exergy conversion processes in the production and end use of transportation fuels, in order to determine the best options for the transportation sector.

O setor de transporte é um exemplo de atividade econômica que depende fundamentalmente das cadeias produtivas do petróleo, gás natural e biocombustíveis para sua operação, além de ser um dos principais consumidores da energia primária do país. Portanto, qualquer melhoria nos processos de produção e uso final dos combustíveis veiculares, repercute favoravelmente tanto na utilização dos recursos energéticos e o desempenho do setor, quanto no impacto ambiental e na economia nacional. Nesse sentido, faz-se necessário o desenvolvimento de uma metodologia que permita avaliar as diferentes rotas de produção e uso final, para determinar as principais fontes de degradação da energia e quantificar o impacto ambiental por meio de uma ferramenta apropriada. Uma valiosa ferramenta é a análise exergética ampliada, a qual provê uma oportunidade de quantificar os requerimentos exergéticos totais e não renováveis e as eficiências globais e, desse modo, perseguir e priorizar o uso daquelas fontes de energia mais favoráveis e amigáveis com o meio ambiente. A exergoeconomia, que visa à distribuição racional dos custos exergéticos entre os diversos produtos de uma mesma planta, usa a quantidade de exergia de cada produto como base para a distribuição da exergia despendida no respectivo processo. Desta forma, neste trabalho se apresenta uma análise comparativa sobre as rotas de produção e uso final dos combustíveis derivados do petróleo e o gás natural (inclusive o hidrogênio produzido da reforma a vapor), etanol, biodiesel, além da análise da geração e distribuição da eletricidade na matriz elétrica brasileira. Propõe-se o uso dos custos exergéticos unitários renováveis e não renováveis e as emissões de CO2 como indicadores para avaliar a intensidade exergética renovável e não renovável, o impacto ambiental e o desempenho termodinâmico no uso final. Este procedimento permite hierarquizar os diferentes processos de conversão de energia na produção e uso final de combustíveis veiculares, a fim de determinar as melhores opções para o setor de transporte. / Transportation sector is an example of economic activity that fundamentally depends on the supply chains of oil, natural gas and biofuels for its operation, as well as being a major consumer of primary energy in the country. Therefore, any improvement that could be achieved in the vehicle fuels production and end use processes, favorably affects both the use of energy resources and industry performance, as well as the environmental impact and the national economy. Accordingly, it is necessary to develop a methodology based on a suitable tool to evaluate the different routes of fuel production and end use, so that the main sources of energy degradation and the environmental impact can be determined and quantified. A valuable tool that serves that purpose is the extended exergy analysis, which provides an opportunity to quantify the total and non-renewable exergy requirements and overall efficiencies, and thereby pursue and prioritize the use of the most environmentally friendly sources of energy. Exergoeconomy, which attempts to rationally distribute the exergy cost among the several products of a single plant, uses the amount of exergy of each product as the basis for the distribution of exergy expended in the respective process. Thus, this work presents a comparative analysis of the production routes and end use of vehicles fuels derived from petroleum and natural gas (including hydrogen produced from methane steam reforming), ethanol, biodiesel, besides of the analysis of generation and distribution of electricity in the Brazilian electricity mix. Moreover, the renewable and non-renewable unit exergy costs and CO2 emissions are proposed as indicators, able to assess the renewable and non-renewable specific exergy consumption, the environmental impact and the thermodynamic performance of transportation sector. This procedure allows to hierarchize the exergy conversion processes in the production and end use of transportation fuels, in order to determine the best options for the transportation sector.

Samtidigt som världens energiproduktion till stor del baseras på förbränning av fossila bränslen behandlas enorma mängder avfall genom deponering. Ökad energiåtervinning av avfall kan bidra till att minska världens utsläpp av växthusgaser. Då avfall bör ses som en resurs är det dock viktigt med en effektiv energiåtervinning. Förbränning i fluidbäddspanna möjliggör god förbränning och hög verkningsgrad men kräver ett finfördelat avfall med lågt innehåll av inert (icke brännbart) material, så kallat RDF. Därför behöver avfallet beredas innan förbränning. En effektiv och välfungerande beredning av avfallsbränsle möjliggör resurseffektiv avfallshantering av utsorterade fraktioner samt effektiv förbränning genom hög bränslekvalitet. Mälarenergis panna 6 på kraftvärmeverket i Västerås är en avfallseldad CFB-panna med bränsleeffekt på omkring 170 MW, vilket motsvarar omkring 50 ton avfall per timme. På den tillhörande bränsleberedningen produceras avfallsbränsle, RDF, i tre beredningslinjer genom att avfallet krossas och olika typer av inert material avskiljs och bildar rejekt från anläggningen.  Magnetisk metall avskiljs med magnetavskiljare, icke-magnetisk metall avskiljs med virvelströmsavskiljare och en tungfraktion bestående av bland annat sten och glas avskiljs med vindsikt. Kvaliteten på avskiljningen är dock bristfällig vilket leder till högt innehåll av inert material i bränslet och högt innehåll av brännbart material i de avskilda fraktionerna. Dessa två problem orsakar kostnader och miljöpåverkan som skulle kunna minskas. Syftet med detta examensarbete var att undersöka vilka faktorer som påverkar avskiljningen av inert material från avfallsbränsle för förbränning i fluidbäddspanna samt ge förslag på åtgärder som kan leda till förbättrad avskiljning. Detta har undersökts genom en fältstudie på den aktuella bränsleberedningen. För att insamla kunskap om bränsleberedningsprocessen och problembilden genomfördes en kartläggning av avskiljningen. Utifrån detta identifierades faktorer som kan påverka avskiljningen. För att ytterligare undersöka vad som påverkar avskiljningsprocessen genomfördes ett antal provtagningar av avskiljningen. En anpassad metod för provtagning av kvaliteten på avskiljningen genom plockanalys togs fram. Sammanlagt genomfördes nio provtagningar under olika förutsättningar. En ny typ av vindsikt testades också för att undersöka hur en investering skulle kunna förbättra avskiljningen. Vindsikten testades utifrån två alternativ av placering. Utifrån resultatet av kartläggningen identifierades fem faktorer som tros påverka avskiljningen. Dessa faktorer är det inkommande avfallet och dess egenskaper, materialflödets storlek genom produktionslinjen, ojämnt materialflöde genom magnetavskiljaren, tillbakakastande turbulens i vindsikten och fastnande material på spjället i vindsikten. Resultatet från de genomförda provtagningarna av kvaliteten på avskiljningen bekräftar att det inkommande avfallet samt materialflödets storlek genom produktionslinjen tros ha stor påverkan på samtliga avskiljare. Då den nya typen av vindsikt testades för att placeras i beredningslinjen visades ingen utmärkande förbättring jämfört med de befintliga vindsiktarna. Då den testades som andra steget i en två-stegs vindsiktning visade däremot resultatet potential att uppnå förbättrad avskiljning. Resultatet visade att två-stegs vindsiktningen har potential att minska mängden tungfraktionsrejekt med cirka 30 – 50 %. Det inerta innehållet i utgående lättfraktion var dock 6 – 8 % vilket motsvarar en höjning av det inerta innehållet i den totala mängden RDF på cirka 0,5 procentenheter. Dock medför en två-stegs vindsiktning att mer material kan siktas ut i vindsiktarna i beredningslinjerna vilket därmed skulle kunna ge en minskning av den totala mängden inert material i RDF. Som slutsats dras att investeringen i ny vindsikt för att skapa en två-stegs vindsiktning skulle kunna ge förbättrad avskiljning. Den nya vindsikten kan med fördel efterföljas av ytterligare avskiljning eftersom mängden inert material i RDF är relativt koncentrerat där. Dock bör en vidare utredning om kostnader och besparingspotential genomföras innan investeringen kan föreslås som åtgärd. Två typer av enklare konstruktioner föreslås för att åtgärda tre av de faktorer som identifierats. En konstruktion för att jämna ut materialflödet innan magnetavskiljaren samt en konstruktion för att förändra luftflödet i vindsikten. Att minska materialflödet genom linjerna föreslås som en viktig åtgärd för att förbättra avskiljningen. Detta kan åstadkommas genom att fördela RDF-produktionen så jämnt som möjligt på produktionslinjerna samt att sprida ut produktionen jämnt över tid. Detta kräver en mer aktiv planering av produktionen samt minimering av stopptider. En viktig slutsats som har dragits är att det inkommande avfallet varierar kraftigt och har stor inverkan på avskiljningsprocessen. En åtgärd som föreslås för att ge förbättrad avskiljning är att en regelbunden kontroll och variation av processen bör införas. Detta föreslås ske genom uttag och kontroll av RDF och rejekt från beredningslinjerna tillsammans med en bedömning av det inkommande avfallet. Informationen bör sedan ligga till grund för ett beslut om hur processen ska styras för att säkerställa en stabil kvalitet på avskiljningen. / Energy recovery of waste got huge potential of decreasing the greenhouse gas emissions in the world. Combustion in fluidized bed boilers gives high resource efficiency but demands a comminuted fuel with low content of inert (non-combustible) materials, a so called refuse derived fuel (RDF).  A well-functioning separation process as part of the RDF-production allows efficient combustion as well as efficient treatment of the separated materials. The purpose of this degree project is to investigate what factors that influences on the separation of inert material from waste for combustion in a fluidized bed boiler and how the separation can be improved. This is investigated through a field study of a fuel-preparation plant in Sweden. The separation process has been examined visually and by experiments based on sampling and manual sorting of waste fractions. The results show five factors that are assumed to influence on the sorting. Three of them are suggested to be solved by simple constructions. One factor that shows to have a great impact is the input waste to the process which is varying to a large extent. A measure that is suggested to give improved separation is a recurrent check of the RDF quality and the reject quality. Combined with information about the input waste this should be basis for recurrent adjustments of the plant to achieve a more stable quality of the separation output. Another measure that is suggested is to decrease the size of the material flow through the production line. This is suggested since the size of the flow is assumed to have an important impact on the separation. The decrease can be achieved by more evenly distribute the production over time and over the production lines. This will though require a more active planning of the production and minimization of production stops. As part of the work a new wind sifter has also been tested.  The wind sifter show good potential of improving the separation if it would be installed to create a two-step wind sifting. However, since the investment of a new wind sifter implies a high investment, a study of the costs and saving potential is required before the investment can be suggested as a measure.