Thesis (doctoral)--Universität Göttingen, 2004. / Includes bibliographical references (p. 411-451) and indexes.

Esta dissertação tem como objetivo apresentar uma estimativa preliminar do volume de recurso contingente não-convencionais de folhelhos oleígenos (oil shale) na Formação Tremembé através de métodos probabilísticos aplicados à informações compiladas de bibliografias existentes sobre a bacia. Como base para esta estimativa utilizou-se informações obtidas através de sísmica 2D, poços existentes na área e perfis geoquímicos. Através da interpretação dos mesmos foram gerados os valores de inputs para os parâmetros utilizados no cálculo, como: espessura econômica, densidade do minério e valor de Ensaio Fisher (Litros de óleo por tonelada de rocha). Para a análise foi construída uma planilha Excel no qual já descrito cada parâmetro do cálculo. Foi utilizado o software @Risk, da Palisade Inc., que é capaz de atribuir distribuições estatísticas a parâmetros utilizados no cálculo obtendo, a partir do método Monte Carlo, distribuições dos possíveis resultados. A metodologia apresentada se demonstra mais adequada ao caso em estudo que o método determinístico, devido a restrição e ausência da precisão dos dados o que aumentaria as incertezas e as chances de erro no cálculo do volume, podendo impossibilitar uma avaliação, no caso do segundo. A metodologia probabilística ao mesmo tempo em que permite uma avaliação preliminar na ausência de dados precisos, ela gera cenários probabilísticos de resultados, possibilitando a antecipação da tomada de decisões em um projeto, permitindo sua continuação ou abandono. / This paper aims to present a preliminary estimate of the volume of unconventional resource (oil shale) in Tremembé Formation, with probabilistic methods applied to previous studies in the basin. The estimate was based on 2D seismic, well and geochemical profiles. The interpretation of these values were generated for the input parameters used in the calculation, such as economic thickness, density and value of the Fisher Assay (liters of oil per tonne of rock). The analysis was done in Excel with a description of each parameter used. The plug-in software @ Risk (Palisade Inc.) was used, enabling statistical distributions and the use of Monte Carlo simulation in the estimate. The methodology proved to be more appropriate to the case study than to the deterministic method, due to restriction and lack of accurate data which would increase the uncertainties and the chances of error in calculating the volume, allowing a preliminary assessment generating distributions probabilistic results, enabling the anticipation of the decision-making process.

Mining activities have a large impact on the environment, for example by the release of heavy metals from acid mine drainage and erosion of mine waste. North-eastern Estonia has the largest commercially exploited oil-shale deposit in the world. Waste from the mining processes have led to contamination of groundwater and streams polluted by phenols, oil products, sulphates and heavy metals. This thesis concerns the metal mobility from oil-shale mines in north-eastern Estonia, through water flow in the drainage system directed into Lake Nõmmejärv, which acts as a sedimentation basin for the mining water. A sediment core along with lake bottom surface samples were retrieved and analysed for heavy metals associated with mining. Water samples were collected and analysed for TOC. The sedimentary records show distinctively the change with the high inflow of water. The analysis of heavy metal content does not suggest a high impact on the environment, possibly because of a buffering effect by the limestone bedrock. The contents of heavy metals are somewhat elevated compared to background contents in Swedish lake sediments, but only cadmium and nickel levels are in the range that can be hazardous for the survival of organisms.

Shale oil is an attractive, alternative fuel source for a world in which there is an increasing demand for energy. However, it is necessary to assess the environmental impacts of the shale oil industry before widescale production is begun. Diversity of retorting processes, the subsequent variability in waste products and the possible waste management schemes makes assessment of these impacts complicated. Waste treatment and disposal are areas which must be researched thoroughly. To properly evaluate the environmental risks associated with the disposal of processed shales and process wastewaters, an appreciation for the sorption/desorption (S/D) characteristics of oil shales is required. The overall objective of this research was to evaluate the S/D capacity of four types of shale: Antrim (spent, eastern shale), Anvil (raw, western shale), Oxy 6 and Run 16 (spent, western shales). Batch and continuous-flow, column experiments were performed in which the S/D behavior of five cations (As, Ca, Cd, Fe, and K) and three anions (F, SO₄, and HCO₃/CO₃) was monitored. The conductivity, redox potential, and pH of the eluent fluids were also determined. This study showed that retort temperature and porosity of the various shales had a significant effect an their S/D characteristics. Batch elution trials with spent shales produced eluents having a characteristic pH in the range 8.5 to 11.5. In these experiments, the shales retorted at lower temperatures (660°C and 793°C) released higher levels of Ca, K, and SO₄ than did a higher temperature, retorted shale (800 to 1000°C) and raw shale. The shales retorted at lower temperatures also had the highest porosities of the four shales and exhibited a greater capacity for sorption of As and F than did the other shales. Continuous-flow, elution trials showed that most inorganics monitored were flushed from the columns of shale in the first 5 to 8 pore volumes of effluent. / Master of Science

La thèse s’intéresse au contrôle de la température d’un front de combustion propagé dans un milieu poreux contenant du carbone fixe et des carbonates (CaCO3). L’objectif principal est de réduire la température, in situ (récupération d’huile ou production de gaz à partir d’un schiste bitumineux) ou dans un procédé (combustion de semicoke), afin de limiter la décarbonatation du milieu et les émissions induites de CO2. Le milieu réactif retenu pour réaliser les expériences en laboratoire est un schiste bitumineux préalablement broyé (0.5 à 2 mm) et pré-pyrolysé, appelé semicoke. Le front est propagé en co-courant. La première technique testée expérimentalement est l’ajout au semicoke d’un matériaux inerte (sable) et/ou d’un matériaux réactif (CaCO3) afin de faire varier le taux de carbone fixe et le taux de CaCO3 et ceci indépendamment. Nous montrons que l’augmentation de CaCO3 permet de baisser la température à 800 °C, mais pas en dessous, ce qui ne permet pas d’éviter la décarbonatation. Faire chuter le contenu en carbone fixe permet de baisser la température du front, voire d’atteindre l’extinction. Aux températures de propagation les plus basses, la décarbonatation est fortement limitée. En revanche le front ralentit car il n’utilise plus tout l’oxygène alimenté. La deuxième technique originale consiste à ajouter du CO2 (20 %molaire) dans l’air de combustion. Nous montrons que dans le cas d’un front chaud, ceci permet de réduire le taux de décarbonatation de 100% à 70%, et d’augmenter en parallèle la production de CO résultant de l’oxydation du carbone fixe, ce qui augmente le PCI du gaz produit. Sur un front plus froid, la décarbonatation qui était de 20% est totalement évitée par l’ajout de CO2. Enfin, des expériences sont proposées dans le mode de combustion “reaction trailing”, très peu connu et mis en oeuvre. Ce mode a l’intérêt majeur d’éviter les réactions de “Lower Temperature Oxidation” préjudiciables au rendement en huile ou en gaz d’un process in situ. Des expériences stables et répétables sont réalisées avec différents pourcentages d’oxygène dans le gaz alimenté. La température du front est directement liée à ce paramètre ; la décarbonatation est clairement limitée dans ce mode de propagation. Deux types de modélisation sont proposés. Un bilan de matière et d’énergie basé sur des expressions analytiques simples permet d’évaluer la température du front et sa vitesse de propagation. Un modèle numérique développé par l’IMFT se base sur des équations de transfert convectif/diffusif de chaleur et de matière, couplées aux réactions d’oxydation du carbone (en CO et en CO2) et de décarbonatation de CaCO3. Il décrit de façon très satisfaisante les expériences en mode “reaction leading” avec variation de la composition du milieu (première technique). / This PhD thesis focuses on the control of the smoldering front propagating in a porous medium containing fixed carbon and carbonates (CaCO3). The main objective is to reduce the front temperature, in situ (oil recovery or gas production from oil shale) or in process (combustion of semicoke), in order to limit the medium decarbonation and the resulting CO2 emissions. The reactive porous medium retained to realize the laboratory experiments is a crushed (0.5 to 2 mm) and pre-pyrolyed oil shale, called semicoke. The front propagates in co-current. The first technique experimentally tested is the addition to the semicoke of an inert material (sand) and/or a reactive material (CaCO3) to vary the contents of fixed carbon and of CaCO3, independently. We show that the increase of the CaCO3 content enables to reduce the temperature to 800 °C, but not below; this does not allow to avoid decarbonation. Bringing down the fixed carbon content enables to reduce the front temperature, see even to reach extinction. In the lowest temperatures of propagation, the decarbonation is strongly limited. On the other hand, the front slows down because it does not use all of the fed oxygen. The second original technique consists in adding CO2 (20 mol.%) to the oxidizer air. We show that for a hot front, the decarbonated fraction is reduced from 100% down to 70%, and the CO production at fixed carbon oxidation is increased; this leads to increase the LCV of the produced gas. For a cold front, the decarbonation which was 20%, is totally avoided by adding CO2. Finely, experiments are proposed in the “reaction trailing” combustion mode, little known and implemented. This mode has the major interest to avoid the reactions of “Lower Temperature Oxidation” prejudicial for oil or gas yields in in situ process. Stable and repeatable experiments are realized with different oxygen fractions in feeding gas. The front temperature is directly linked to this parameter; the decarbonation is clearly limited in this mode of propagation. Two types of modeling are proposed. A mass and thermal balance based on simple analytical expressions enables to evaluate the front temperature and velocity. A numerical model developed by IMFT is based on convective/diffusive heat and mass transfer equations coupled with the oxidation reactions (into CO and CO2) and CaCO3 decarbonation is proposed. It describes in a very satisfactory way the experiments in the “reaction leading” mode with variation of the medium composition (first technique).

Estonia is the only country in the world, which is totally dependent on oil shale in its energy system. Although this fossil fuel exists in enormous quantities around the world, it has so far not been utilized on a larger scale. The reasons for this have been both economic and, in recent times, ecological. It can therefore be argued that in most cases, oil shale represents an inferior solution compared to other energy sources. This work examines why a technology utilizing oil shale has developed in Estonia and why Estonia appears not to be in a position to switch to other energy sources. In this work it is claimed that oil shale actually has been an appropriate solution to short-term concerns, despite the fact that its long-term drawbacks have been identified. These circumstances led to path dependence. Once the technology was in place, it advanced along its learning curve producing a satisfactory outcome, but not an optimal one. However, this situation has been accepted due to the extremely turbulent institutional environment Estonia has undergone in the 20th century. In Sweden, a somewhat similar (but smaller) oil shale industry was shut down in the 1960s because of poor economic performance, but also because of the competition from other energy sources. Such competition did not take place in Estonia, in part due to the specific institutional set-up of the Soviet Union. This made it possible for the Estonian oil shale industry to develop further, causing the present lock-in. Today the existing infrastructure, the knowledge-base, and the particular socio-political circumstances of Estonia effectively prevent change. Furthermore, it is argued that because there was only little oil shale-related technology developed outside Estonia, most technology had to be developed domestically. This in turn has forced the Estonian oil shale industry to make several highly inconvenient alliances in order to gain room to manoeuvre. Partially as a result of this, there is today wide-spread scepticism towards the industry, but no exit in sight in the foreseeable future. One purpose of this work is to contribute to a broader understanding why human societies have become dependent on fossil fuels and to extend our knowledge on where to search for an exit.

Multistage hydraulic fracturing of horizontal wells continues to be a major technological tool in the oil and gas industry. Creation of multiple transverse fractures in shale gas has enabled production from very low permeability. The strategy entails the development of a Stimulated Reservoir Volume (SRV), defined as the volume of reservoir, which is effectively stimulated to increase the well performance. An ideal model for a shale gas SRV is a rectangle of length equal to horizontal well length and width equal to twice the half length of the created hydraulic fractures. This project focused on using the Multistage Transverse Fractured Horizontal Wells (MTFHW) for two novel applications. The first application considers using the SRV of a shale gas well, after the gas production rate drops below the economic limit, for low grade geothermal heat extraction. Cold water is pumped into the fracture network through one horizontal well drilled at the fracture tips. Heat is transferred to the water through the fracture surface. The hot water is then recovered through a second horizontal well drilled at the other end of the fracture network. The basis of this concept is to use the already created stimulated reservoir volume for heat transfer purposes. This technique was applied to the SRV of Haynesville Shale and the results were discussed in light of the economics of the project. For the second application, we considered the use of a similarly created SRV for producing hydrocarbon products from oil shale. Thermal decomposition of kerogen to oil and gas requires heating the oil shale to 700 degrees F. High quality saturated steam generated using a small scale nuclear plant was used for heating the formation to the necessary temperature. Analytical and numerical models are developed for modeling heat transfer in a single fracture unit of MTFHW. These models suggest that successful reuse of Haynesville Shale gas production wells for low grade geothermal heat extraction and the project appears feasible both technically and economically. The economics of the project is greatly aided by eliminating well drilling and completion costs. The models also demonstrate the success of using MTFHW array for heating oil shale using SMR technology.

Thesis (doctoral)--Universität Göttingen, 2004. / Includes bibliographical references (p. 411-451) and indexes.

Conselho Nacional de Desenvolvimento Científico e Tecnológico / The impact of retorted oil shale (ROS) addition on the dynamics of carbon (C) of crop residues (CR) in the soil is little known. Under laboratory conditions, the present study aimed to evaluate the residual and immediate effects of ROS on C mineralization of CR, water stability aggregates and storage C in the particulate (>53 μm) and associated minerals fractions (<53μm) of organic matter (OM) of a Hapludalf. In experiment 1, treatments consisted of soil samples from plots that received four additions of ROS, totaling 0, 6,000 and 12,000 kg ha-1. In experiment 2, treatments consisted of soil with no history of application of ROS (0 kg ha-1), that in the laboratory received three doses of ROS (0, 1,500 and 3,000 kg ha-1). In both experiments, the treatments were evaluated in the presence (3,000 kg ha-1) and absence of leaves and stalks of soybeans. The release of C-CO2 was evaluated for 80 days and at the end of the experiment determined the aggregate stability and C storage in different OM fractions. The addition of CR in soil with a history of ROS addition did not alter the release of C-CO2 and also did not reduce the apparent mineralization of C of RC compared to addition of these residues in soil with no history. In experiment 2, there was a reduction in the release of C-CO2 compared to the control only the treatment with stalks + 3000 kg ROS ha-1. In experiment 2, the treatment stalks + 3000 kg ROS ha-1 provided an increase in aggregate stability compared with treatment with only stalks. In experiment 1, the ROS addition tended to higher retention of C stalks and leaves in the soil. In experiment 2, the application of CR + ROS promoted greater retention of soil C only in the treatment with leaves. Under laboratory conditions, the soil with a history of ROS addition did not affect mineralization and retention of crop residue C added to soil. Besides, the ROS showed an immediate effect, reducing C mineralization from stalks and increasing retention of C from leaves added to the soil. / O impacto da adição de xisto retortado (XR) sobre a dinâmica do carbono (C) de resíduos culturais (RC) no solo é pouco conhecido. Em condições de laboratório, o presente estudo objetivou avaliar o efeito residual e imediato do XR sobre a mineralização do C de RC, estabilidade de agregados em água e armazenamento de C nas frações particulada (>53 μm) e associada aos minerais (<53 μm) da matéria orgânica (MO) de um Argissolo Vermelho Distrófico arênico. No experimento 1, os tratamentos foram compostos por amostras de solo de parcelas que receberam quatro aplicações de XR, totalizando 0, 6.000 e 12.000 kg ha-1. Já no experimento 2, os tratamentos foram constituídos com solo somente da parcela sem histórico de aplicação de XR (0 kg ha-1), que no laboratório recebeu três doses de XR equivalentes a 0, 1.500 e 3.000 kg ha-1. Em ambos os experimentos os tratamentos foram avaliados na presença (3.000 kg ha-1) e ausência de folhas e talos de soja. A liberação de C-CO2 foi avaliada durante 80 dias e ao final do experimento determinados a estabilidade de agregados e o armazenamento de C nas diferentes frações da MO. A adição de RC no solo com histórico de adição de XR não alterou a liberação de C-CO2 e também não reduziu a mineralização aparente do C dos RC comparado a adição desses resíduos em solo sem histórico. No experimento 2, houve redução na liberação de C-CO2 em relação ao controle somente no tratamento com talos + 3.000 kg de XR ha-1. No experimento 2, o tratamento talos + 3.000 kg de XR ha-1 proporcionou incremento na estabilidade de agregados em comparação com o tratamento somente com talos. No experimento 1, a adição de XR apresentou tendência de maior retenção de C dos talos e folhas no solo. No experimento 2, a aplicação conjunta de resíduos e XR promoveu maior retenção de C no solo apenas no tratamento com folhas. Em condições de laboratório, o solo com histórico de aplicação de XR não afetou a mineralização e a retenção do C de resíduos culturais adicionados ao solo. Além disso, o XR apresentou efeito imediato, reduzindo a mineralização do C de talos e aumentando a retenção do C de folhas adicionadas ao solo.

Orientador: Antonio Carlos Luz Lisboa / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-06T19:43:19Z (GMT). No. of bitstreams: 1 Porto_PauloSergiodaSilva_D.pdf: 16531970 bytes, checksum: 29f4837be6b441e6118e76a89e91a0ab (MD5) Previous issue date: 2005 / Resumo: Xisto pirobetuminoso é uma rocha sedimentar que contém querogênio, um material orgânico que se encontra disseminado em sua estrutura mineral. O querogênio é extraído por aquecimento a altas temperaturas, em reatores conhecidos como retortas, 1iberando óleo e gás. Este óleo quando refinado produz destilados com as mesmas características encontradas nos de petróleo, sendo considerado uma fonte de energia alternativa. A existência de umidade no xisto na entrada do reator gera uma zona de secagem influenciando na redução da temperatura dos gases e diminuição da eficiência da retorta. O objetivo deste trabalho é investigar a perda de umidade durante a secagem de partículas de xisto, visando conhecer os mecanismos envolvidos. Para obter o perfil de umidade ao longo do tempo foram utilizadas partículas classificadas em três diferentes lotes quanto ao diâmetro médio de partícula (dp): partículas individuais do Lote A (dp = 80 mm e dp = 60 mm); partículas do Lote B que subdivide-se em quatro sublotes (~ = 5,3 mm, dp = 3 mm, dp = 1,5 mm e dp = 0,85 mm) e partículas do Lote C (dp < 0,074 mm). Os experimentos de secagem foram realizados em diversos secadores: partículas do Lote A secas em estufa com circulação de ar a 60°C e 90°C; partículas do Lote B secas em bandeja termogravimétrica a 40°C, 60 °c, 80°C e 100°C e em leito de jorro e leito fluidizado a 50°C e 70°C; partículas do Lote C secas em um analisador termogravimétrico, cujas temperaturas iniciais de 20°C variaram ao longo do tempo até atingir valores máximos de 40 °C, 70°C e 100°C. Exceto os experimentos realizados no ana1isador termogravimétrico, em todos os demais a temperatura foi mantida constante. Utilizou-se o modelo matemático de difusão de Fick, considerando geometrias uni e tri-dimensionais. Na solução destes modelos foram desenvolvidos programas em linguagem Fortran para descrever a variação de umidade das partículas de xisto ao longo do tempo e da posição, levando-se em conta a geometria da partícula e a temperatura do ar de secagem (constante ou variável). Os resultados preditos pelos modelos foram comparados com os experimentais apresentando boa concordância. Estes modelos podem contribuir na estimativa de parâmetros desconhecidos do processo. Quanto ao leito em jorro e leito fiuidizado, verificou-se que são técnicas adeqüadas para a secagem de xisto / Abstract: Oil shale is a sedimentary rock which contains kerogen, an organic matter scattered througout a mineral matrix. Kerogen is extracted by pyrolysis at high temperatures in reactors known as retorts producing oil and gas. The oil, when refined, produces distillates with the same characteristics as petroleum. Oil shale is considered an alternative energy source to petroleum. At the top of a moving bed retort oil shale moisture vaporization consumes energy, thereby reducing the retort efficiency. Oil shale drying has been investigated to optimize pyrolysis. The objective of this work was to investigate the moisture loss during oil shale particles drying to know the mechanisms involved. In order to obtain the moisture profile with time particles classified in three different categories / Doutorado / Engenharia de Processos / Doutor em Engenharia Química