A contribution towards the performance and structural understanding of copper and nickel salts as ammonia stores

The ongoing depletion of fossil fuels and the severe consequences of the greenhouse effect make the development of alternative energy systems crucially important. While hydrogen is, in principle, a promising alternative, releasing nothing but energy and pure water. Hydrogen storage is complicated and no completely viable technique has been proposed so far. This work is concerned with the study of one potential alternative to pure hydrogen: ammonia, and more specifically its storage in solids. Ammonia, NH3, can be regarded as a chemical hydrogen carrier with the advantages of strongly reduced flammability and explosiveness as compared to hydrogen. Furthermore, ammine metal salts presented here as promising ammonia stores easily store up to 50 wt.-% ammonia, giving them a volumetric energy density comparable to natural gas. The model system NiX2–NH3 ( X = Cl, Br, I) is studied thoroughly with respect to ammine salt formation, thermal decomposition, air stability and structural effects. The system CuX2–NH3 ( X = Cl, Br) has an adverse thermal decomposition behaviour, making it impractical for use as an ammonia store. This system is, however, most interesting from a structural point of view and some work concerning the study of the structural behaviour of this system is presented. Finally, close chemical relatives to the metal ammine halides, the metal ammine nitrates are studied. They exhibit interesting anion arrangements, which is an impressive showcase for the combination of diffraction and spectroscopic information. The characterisation techniques in this thesis range from powder diffraction over single crystal diffraction, spectroscopy, computational modelling, thermal analyses to gravimetric uptake experiments. Further highlights are the structure solutions and refinements from powder data of (NH4)2[NiCl4(H2O)(NH3)] and Ni(NH3)2(NO3)2, the combination of crystallographic and chemical information for the elucidation of the (NH4)2[NiCl4(H2O)(NH3)] formation reaction and the growth of single crystals under ammonia flow, a technique allowing the first documented successful growth and single crystal diffraction measurement for [Cu(NH3)6]Cl2.

Analysis of cogeneration in the present energy framework

In this paper, a general vision of cogeneration penetration in the European Union is shown; after this, a case study is included, evaluating as a function of two factors (electricity and emission allowance prices) the suitability of installing, for an industry with a determined thermal demand, two different options. The first one is a gas turbine cogeneration plant generating steam through a heat recovery steam generator (HRSG). The second one consists of installing a natural gas boiler for steam production covering the electricity demand from the grid. The CO2 emissions from both options are compared regarding different kinds of generation mixes from the electricity grid in the case of using the industrial boiler; taking into account the advantages of using biomass in relation to emissions, a last comparison has been carried out considering a biomass boiler instead of the natural gas boiler.

Pricing derivatives with stochastic volatility

This Ph.D. thesis contains 4 essays in mathematical finance with a focus on pricing Asian option (Chapter 4), pricing futures and futures option (Chapter 5 and Chapter 6) and time dependent volatility in futures option (Chapter 7). In Chapter 4, the applicability of the Albrecher et al.(2005)'s comonotonicity approach was investigated in the context of various benchmark models for equities and com- modities. Instead of classical Levy models as in Albrecher et al.(2005), the focus is the Heston stochastic volatility model, the constant elasticity of variance (CEV) model and the Schwartz (1997) two-factor model. It is shown that the method delivers rather tight upper bounds for the prices of Asian Options in these models and as a by-product delivers super-hedging strategies which can be easily implemented. In Chapter 5, two types of three-factor models were studied to give the value of com- modities futures contracts, which allow volatility to be stochastic. Both these two models have closed-form solutions for futures contracts price. However, it is shown that Model 2 is better than Model 1 theoretically and also performs very well empiri- cally. Moreover, Model 2 can easily be implemented in practice. In comparison to the Schwartz (1997) two-factor model, it is shown that Model 2 has its unique advantages; hence, it is also a good choice to price the value of commodity futures contracts. Fur- thermore, if these two models are used at the same time, a more accurate price for commodity futures contracts can be obtained in most situations. In Chapter 6, the applicability of the asymptotic approach developed in Fouque et al.(2000b) was investigated for pricing commodity futures options in a Schwartz (1997) multi-factor model, featuring both stochastic convenience yield and stochastic volatility. It is shown that the zero-order term in the expansion coincides with the Schwartz (1997) two-factor term, with averaged volatility, and an explicit expression for the first-order correction term is provided. With empirical data from the natural gas futures market, it is also demonstrated that a significantly better calibration can be achieved by using the correction term as compared to the standard Schwartz (1997) two-factor expression, at virtually no extra effort. In Chapter 7, a new pricing formula is derived for futures options in the Schwartz (1997) two-factor model with time dependent spot volatility. The pricing formula can also be used to find the result of the time dependent spot volatility with futures options prices in the market. Furthermore, the limitations of the method that is used to find the time dependent spot volatility will be explained, and it is also shown how to make sure of its accuracy.

Active site engineering for heterogeneous catalysis using emerging nano-structured materials

The growing concern about the depletion of oil has spurred worldwide interest in finding alternative feedstocks for important petrochemical commodities and fuels. On the one hand, the enormous re-serves found (208 trillion cubic feet proven1), environmental sustainability and lower overall costs point to natural gas as the primary source for energy and chemicals in the near future.2 Nowadays the transformation of methane into useful chemicals and liquid fuels is only feasible via synthesis gas, a mixture of molecular hydrogen and carbon monoxide, that is further transformed to methanol or to hydrocarbons under moderate reaction conditions (150-350 °C and 10-100 bar).3 For a major cost reduction and in order to valorize small natural gas sources, either more efficient "syngas to products" catalysts should be produced or the manner in which methane is initially activated should be changed, ideally by developing catalysts able to directly oxidize methane to interesting products such as methanol. On the other hand, from the point of view of CO2 emissions, the use of the re-maining fossil resources will further contribute to global warming. In this scenario, the development of efficient routes for the transformation of CO2 into useful chemicals and fuels would represent a considerable step forward towards sustainability. Indeed, the environmental and economic incen-tives to develop processes for the conversion of CO2 into fuels and chemicals are great. However, for such conversions to become economically feasible, considerable research is necessary. In this lecture we will summarize our recent efforts into the design of new catalytic systems, based on MOFs and COFs, to address these challenges. Examples include the development of new Fe based FTS catalysts, electrocatalysts for the selective conversion of CO2 into syngas, the development of efficient catalysts for the utilization of formic acid as hydrogen storage vector and the development of new enzyme inspired systems for the direct transformation of methane to methanol under mild reaction conditions. References (1) http://www.clearonmoney.com/dw/doku.php?id=public:natural_gas_reserves. (2) Derouane, E. G.; Parmon, V.; Lemos, F.; Ribeiro, F. R. Sustainable Strategies for the Up-grading of Natural Gas: Fundamentals, Challenges, and Opportunities; Springer, 2005. (3) Rofer-DePoorter, C. K. Chemical Reviews. ACS Publications 1981, pp 447–474.

Síntese e caracterização de NiO-CGO para anodo e eletrólitos sólidos e base de Céria para SOFC

The direct use of natural gas makes the Solid Oxide Fuel Cell (SOFC) potentially more competitive with the current energy conversions technologies. The Intermediate Temperature SOFC (IT-SOFC) offer several advantages over the High Temperature SOFC (HT-SOFC), which includes better thermal compatibility among components, fast start with lower energy consumption, manufacture and operation cost reduction. The CeO2 based materials are alternatives to the Yttria Stabilized Zirconia (YSZ) to application in SOFC, as they have higher ionic conductivity and less ohmic losses comparing to YSZ, and they can operate at lower temperatures (500-800°C). Ceria has been doped with a variety of cations, although, the Gd3+ has the ionic radius closest to the ideal one to form solid solution. These electrolytes based in ceria require special electrodes with a higher performance and chemical and termomechanical compatibility. In this work compounds of gadolinia-doped ceria, Ce1-xGdxO2-δ (x = 0,1; 0,2 and 0,3), used as electrolytes, were synthesized by polymeric precursors method, Pechini, as well as the composite material NiO - Ce0,9Gd0,1O1,95, used as anode, also attained by oxide mixture method, mixturing the powders of the both phases calcinated already. The materials were characterized by X ray diffraction, dilatometry and scanning electronic microscopy. The refinement of the diffraction data indicated that all the Ce1-xGdxO2-δ powders were crystallized in a unique cubic phase with fluorite structure, and the composite synthesized by Pechini method produced smaller crystallite size in comparison with the same material attained by oxide mixture method. All the produced powders had nanometric characteristics. The composite produced by Pechini method has microstructural characteristics that can increase the triple phase boundaries (TPB) in the anode, improving the cell efficiency, as well as reducing the mass transport mechanism effect that provokes anode degradation

Sinterização de Ce1-XEuXO2-(X/2) para aplicação como eletrólito sólido em células a combustível de temperaturas intermediárias

Given the environmental concern over global warming that occurs mainly by emission of CO2 from the combustion of petroleum, coal and natural gas research focused on alternative and clean energy generation has been intensified. Among these, the highlight the solid oxide fuel cell intermediate temperature (IT-SOFC). For application as electrolyte of the devices doped based CeO2 with rare earth ions (TR+ 3) have been quite promising because they have good ionic conductivity and operate at relatively low temperatures (500-800 ° C). In this work, studied the Ce1-xEuxO2-δ (x = 0,1, 0,2 and 0,3), solid solutions synthesized by the polymeric precursor method to be used as solid electrolyte. It was also studied the processing steps of these powders (milling, compaction and two step sintering) in order to obtain dense sintered pellets with reduced grain size and homogeneous microstructure. For this, the powders were characterized by thermal analysis, X-ray diffraction, particle size distribution and scanning electrons microscopy, since the sintered samples were characterized by dilatometry, scanning electrons microscopy, density and grain size measurements. By x-ray diffraction, it was verified the formation of the solid solution for all compositions. Crystallites in the nanometric scale were found for both sintering routes but the two step sintering presented significant reduction in the average grain size

OBSERVATIONS AND EMISSIONS OF ENERGY-ASSOCIATED OZONE PRECURSORS IN THE MID-ATLANTIC UNITED STATES

Surface ozone is formed in the presence of NOx (NO + NO2) and volatile organic compounds (VOCs) and is hazardous to human health. A better understanding of these precursors is needed for developing effective policies to improve air quality. To evaluate the year-to-year changes in source contributions to total VOCs, Positive Matrix Factorization (PMF) was used to perform source apportionment using available hourly observations from June through August at a Photochemical Assessment Monitoring Station (PAMS) in Essex, MD for each year from 2007-2015. Results suggest that while gasoline and vehicle exhaust emissions have fallen, the contribution of natural gas sources to total VOCs has risen. To investigate this increasing natural gas influence, ethane measurements from PAMS sites in Essex, MD and Washington, D.C. were examined. Following a period of decline, daytime ethane concentrations have increased significantly after 2009. This trend appears to be linked with the rapid shale gas production in upwind, neighboring states, especially Pennsylvania and West Virginia. Back-trajectory analyses similarly show that ethane concentrations at these monitors were significantly greater if air parcels had passed through counties containing a high density of unconventional natural gas wells. In addition to VOC emissions, the compressors and engines involved with hydraulic fracturing operations also emit NOx and particulate matter (PM). The Community Multi-scale Air Quality (CMAQ) Model was used to simulate air quality for the Eastern U.S. in 2020, including emissions from shale gas operations in the Appalachian Basin. Predicted concentrations of ozone and PM show the largest decreases when these natural gas resources are hypothetically used to convert coal-fired power plants, despite the increased emissions from hydraulic fracturing operations expanded into all possible shale regions in the Appalachian Basin. While not as clean as burning natural gas, emissions of NOx from coal-fired power plants can be reduced by utilizing post-combustion controls. However, even though capital investment has already been made, these controls are not always operated at optimal rates. CMAQ simulations for the Eastern U.S. in 2018 show ozone concentrations decrease by ~5 ppb when controls on coal-fired power plants limit NOx emissions to historically best rates.

La interdependencia hispano-argelina en cuestiones energéticas

Desde los años 1980 España y Europa importan una parte creciente de sus hidrocarburos de Argelia. Esta situación ha llevado a una interdependencia que puede resultar peligrosa por ambas partes. España no consigue reducir su consumo de hidrocarburos, pero en su esfuerzo por diversificar e independizarse del petróleo ha incrementado significativamente el consumo de gas natural procedente de Argelia. Por su parte este país ha aumentado sus reservar en divisas lo que le ha permitido mejorar extraordinariamente su situación desde la guerra civil de los años 1990 y garantizar a corto plazo el estatus quo social y político. Sin embargo esa misma dependencia de los hidrocarburos le impide resolver los graves problemas estructurales de su juventud y de una economía rentista. Esta comunicación estudia estas dependencias analizando la creciente complejidad del mercado de los hidrocarburos, los esfuerzos españoles por diversificar sus fuentes de abastecimiento y las apuestas de Argelia por continuar suministrando energía primaria.

Os Estados Unidos da América e a Revolução do Shale

Ao longo dos últimos anos, tem-se verificado grandes mudanças no mercado energético global, sendo os Estados Unidos da América um dos grandes protagonistas. A presente investigação tem como principal objetivo compreender e clarificar o conceito de independência energética/auto-suficiência energética e averiguar a possibilidade e o alcance deste propósito por parte dos Estados Unidos da América, desde a Revolução do Shale. Ao longo desta investigação haverá oportunidade de estudar as políticas energéticas assumidas durante aproximadamente os últimos 40 anos, obter informações sobre a segurança energética dos Estados Unidos, bem como formas de exploração energética americana, política para exportação de energia e impactos geopolíticos. Facilmente se observa ao longo deste trabalho que a auto-suficência não pode ser vista numa perspetiva de criação de condições para o isolacionismo americano mas sim numa perspetiva de instrumentalização e proteção dos seus aliados.

Estudo de massa cerâmica triaxial visando à otimização do ciclo de queima da indústria de cerâmica estrutural

Over recent years the structural ceramics industry in Brazil has found a very favorable market for growth. However, difficulties related to productivity and product quality are partially inhibiting this possible growth. An alternative for trying to solve these problems and, thus, provide the pottery industry the feasibility of full development, is the substitution of firewood used in the burning process by natural gas. In order to contribute to this process of technological innovation, this paper studies the effect of co-use of ceramic phyllite and kaolin waste on the properties of a clay matrix, verifying the possible benefits that these raw materials can give to the final product, as well as the possibility of such materials to reduce the heat load necessary to obtain products with equal or superior quality. The study was divided into two steps: characterization of materials and study of formulations. Two clays, a phyllite and a residue of kaolin were characterized by the following techniques: laser granulometry, plasticity index by Atterberg limits, X-ray fluorescence, X-ray diffraction, mineralogical composition by Rietveld, thermogravimetric and differential thermal analysis. To study the formulations, specifically for evaluation of technological properties of the parts, was performed an experimental model that combined planning involving a mixture of three components (standard mass x phyllite x kaolin waste) and a 23 factorial design with central point associated with thermal processing parameters. The experiment was performed with restricted strip-plot randomization. In total, 13 compositional points were investigated within the following constraints: phyllite ≤ 20% by weight, kaolin waste ≤ 40% by weight, and standard mass ≥ 60% by weight. The thermal parameters were used at the following levels: 750 and 950 °C to the firing temperature, 5 and 15 °C/min at the heating rate, 15 and 45min to the baseline. The results showed that the introduction of phyllite and/or kaolin waste in ceramic body produced a number of benefits in properties of the final product, such as: decreased absorption of water, apparent porosity and linear retraction at burn; besides the increase in apparent specific mass and mechanical properties of parts. The best results were obtained in the compositional points where the sum of the levels of kaolin waste and phyllite was maximal (40% by weight), as well as conditions which were used in firing temperatures of 950 °C. Regarding the prospect of savings in heat energy required to form the desired microstructure, the phyllite and the residue of kaolin, for having small particle sizes and constitutions mineralogical phases with the presence of fluxes, contributed to the optimization of the firing cycle.

Avaliação do potencial energético de cana (Arundo donax L.) no Algarve

Dissertação de Mestrado, Energias Renováveis e Gestão de Energia, Faculdade de Ciências e Tecnologia, Universidade do Algarve, 2016

Efeito da velocidade de aquecimento nas propriedades de produtos da cerâmica estrutural

Heating rate is one of the main variables that determine a fire cycle. In industrial processes that use high temperatures, greater fire great can reduce the cost of production and increase productivity. The use of faster and more efficient fire cycles has been little investigated by the structural ceramic industry in Brazil. However, one of the possibilities that aims at modernizing the sector is the use of roller kilns and the inclusion of natural gas as fuel. Thus, the purpose of this study is to investigate the effect of heating rate on the technological properties of structural ceramic products. Clay raw materials from the main ceramic industries in the state of Rio Grande do Norte were characterized. Some of the raw materials characterized were formulated to obtain the best physical and mechanical properties. Next, raw materials and formulations were selected to study the influence of heating rate on the final properties of the ceramic materials. The samples were shaped by pressing and extrusion and submitted to rates of 1 °C/min, 10 °C/min and 20 °C/min, with final temperatures of 850 °C, 950 °C and 1050 °C. Discontinuous cycles with rates of 10 °C/min or 15 °C/min up to 600 °C and a rate of 20 °C/min up to final temperature were also investigated. Technological properties were determined for all the samples and microstructural analysis was carried out under a number of fire conditions. Results indicate that faster and more efficient fire cycles than those currently in practice could be used, limiting only some clay doughs to certain fire conditions. The best results were obtained for the samples submitted to slow cycles up to 600 °C and fast fire sinterization up to 950 °C. This paper presents for the first time the use of a fast fire rate for raw materials and clay formulations and seeks to determine ideal dough and processing conditions for using shorter fire times, thus enabling the use of roller kilns and natural gas in structural ceramic industries

Análise paramétrica da simulação composicional do processo de Drenagem Gravitacional Assistida por Gás (GAGD)

In Brazil and around the world, oil companies are looking for, and expected development of new technologies and processes that can increase the oil recovery factor in mature reservoirs, in a simple and inexpensive way. So, the latest research has developed a new process called Gas Assisted Gravity Drainage (GAGD) which was classified as a gas injection IOR. The process, which is undergoing pilot testing in the field, is being extensively studied through physical scale models and core-floods laboratory, due to high oil recoveries in relation to other gas injection IOR. This process consists of injecting gas at the top of a reservoir through horizontal or vertical injector wells and displacing the oil, taking advantage of natural gravity segregation of fluids, to a horizontal producer well placed at the bottom of the reservoir. To study this process it was modeled a homogeneous reservoir and a model of multi-component fluid with characteristics similar to light oil Brazilian fields through a compositional simulator, to optimize the operational parameters. The model of the process was simulated in GEM (CMG, 2009.10). The operational parameters studied were the gas injection rate, the type of gas injection, the location of the injector and production well. We also studied the presence of water drive in the process. The results showed that the maximum vertical spacing between the two wells, caused the maximum recovery of oil in GAGD. Also, it was found that the largest flow injection, it obtained the largest recovery factors. This parameter controls the speed of the front of the gas injected and determined if the gravitational force dominates or not the process in the recovery of oil. Natural gas had better performance than CO2 and that the presence of aquifer in the reservoir was less influential in the process. In economic analysis found that by injecting natural gas is obtained more economically beneficial than CO2

Estudo de adsorvente obtido de terras diatomáceas para remoção de metais pesados em águas produzidas: processamento, caracterização e dinâmica em leito fixo

The acceleration of industrial growth in recent decades on all continents aroused the interest of the companies to counter the impacts produced on the environment, spurred primarily by major disasters in the petroleum industry. In this context, the water produced is responsible for the largest volume of effluent from the production and extraction of oil and natural gas. This effluent has in its composition some critical components such as inorganic salts, heavy metals (Fe, Cu, Zn, Pb, Cd, ), presence of oil and chemicals added in the various production processes. In response to impact, have been triggered by research alternative adsorbent materials for water treatment and water produced, in order to removing oils and acids and heavy metals. Many surveys of diatomaceous earth (diatomite) in Brazil involve studies on the physico-chemical, mineral deposits, extraction, processing and applications. The official estimated Jazi are around 2.5 million tonnes, the main located in the states of Bahia (44%) and Rio Grande do Norte (37,4%). Moreover, these two states appear as large offshore producers, earning a prominent role in research of adsorbents such as diatomite for treatment of water produced. Its main applications are as an agent of filtration, adsorption of oils and greases, industrial load and thermal insulator. The objective of this work was the processing and characterization of diatomite diatomaceous earth obtained from the municipality of Macaíba-RN (known locally as tabatinga) as a low cost regenerative adsorbent for removal of heavy metals in the application of water produced treatment. In this work we adopted a methodology for batch processing, practiced by small businesses located in producing regions of Brazil. The characterization was made by X-ray diffraction (XRD), scanning electron microscopy (SEM) and specific surface area (BET). Research conducted showed that the improvement process used was effective for small volume production of diatomite concentrated. The diatomite obtained was treated by calcination at temperature of 900 oC for 2 hours, with and without fluxing Na2CO3 (4%), according to optimal results in the literature. Column adsorption experiments were conducted to percolation of the in nature, calcined and calcined fluxing diatomites. Effluent was used as a saline solution containing ions of Cu, Zn, Na, Ca and Mg simulating the composition of produced waters in the state of Rio Grande do Norte, Brazil. The breakthrough curves for simultaneous removal of copper ions and zinc as a result, 84.3% for calcined diatomite and diatomite with 97.3 % for fluxing. The calcined fluxing diatomite was more efficient permeability through the bed and removal of copper and zinc ions. The fresh diatomite had trouble with the permeability through the bed under the conditions tested, compared with the other obtained diatomite. The results are presented as promising for application in the petroleum industry

Análise das emissões gasosas de um veículo flex funcionando com diferentes combustíveis

Efforts in research and development of new technologies to reduce emission levels of pollutant gases in the atmosphere has intensified in the last decades. In this context, it can be highlighted the modern systems of electronic engine management, new automotive catalysts and the use of renewable fuels which contributes to reduce the environmental impact. The purpose of this study was a comparative analysis of gas emissions from a automotive vehicle, operating with different fuels: natural gas, AEHC or gasoline. To execute the experimental tests, a flex vehicle was installed on a chassis dynamometer equipped with a gas analyzer and other complementary accessories according to the standard guidelines of emission and security procedures. Tests were performed according to NBR 6601 and NBR 7024, which define the urban and road driving cycle, respectively. Besides the analysis of exhaust gases in the discharge tube, before and after the catalyst, using the suction probe of the gas analyzer to simulate the vehicle in urban and road traffic, were performed tests of fuel characterization. Final results were conclusive in indicating leaded gasoline as the fuel which most contributed with pollutant emissions in atmosphere and the usual gasoline being the fuel which less contributed with pollutant emissions in atmosphere