The technique of Inverse Gas Chromatography (IGC) was employed for the study of the interactions between various organic solvents with various types of the major inorganic materials (clay minerals and sand) found in Albertas oil sands. Heat of adsorption (-H) was measured for each solvent with respect to each of the four studied inorganic materials. The calculation we used was based on the Infinite Dilution Thermodynamics approach used by Katsanos et. al. [Journal of Chromatography A. 795, 133-184 (1998)]. Retention time data is converted into Retention Volume; H is then obtained by a plot vs. 1/T. The solvents studied were straight chain, branched and cyclic alkanes, alkenes, aromatics, and ketones. The inorganic materials studied were kaolinite, illite, illite-smectite mixed layer, and sand. Our results show that solvents had significantly less affinity for sand when compared to the three types of clay studied. Additionally, solvent affinity to illite had appreciable difference when compared to kaolinite and the mixed layer of illite-smectite. Furthermore, increase in carbon number leads to increased adsorption to the clay. Branched or cyclic alkanes have slightly lower adsorption to clay when compared to straight chain alkane of the same carbon number. Double bonds significantly increase solvent affinity to clay, but have no effect on sand. Lastly, alcohols and ketones have very high affinity to clay that no elution occurred when either solvent was injected into the GC and only ketone eluted when sand was the stationary phase in the GC column. / Chemical Engineering

Thesis (M.S.)--West Virginia University, 2006. / Title from document title page. Document formatted into pages; contains vii, 60 p. : ill. Includes abstract. Includes bibliographical references.

Techn. Universiẗat, Diss., 2003--Darmstadt.

Le recyclage des matériaux routiers constitue une voie de développement durable qui présente des bénéfices en termes de consommation d’énergie et de ressources non renouvelables. Pour mieux prédire les propriétés finales de ces matériaux, la compréhension des phénomènes de mélange intervenant lors de la fabrication des enrobés à chaud et à tiède en centrale d’enrobage est indispensable. L’objectif de la thèse est donc de comprendre et d’identifier les facteurs influençant les phénomènes de mouillage, de remobilisation et de miscibilité des liants bitumineux. Pour cela, la démarche d’étude choisie consiste à étudier les interactions locales entre les constituants organiques et inorganiques du mélange selon une approche physico-chimique aux interfaces et interphases. Concernant le mouillage, des indicateurs ont été sélectionnés pour suivre son évolution à l’interface bitume/roche polie. L’influence du vieillissement du liant a aussi été prise en compte. La viscosité et le taux d’asphaltènes des bitumes ainsi que la composition de surface du substrat minéral influencent la qualité de mouillage. Les résultats ont montré que les évolutions étaient régies par un modèle applicable aux surfaces polies, poreuses et chimiquement hétérogènes. La remobilisation du liant vieilli (à température réduite) par le liant d’apport (chauffé à 160°C) a été étudiée à l’interface et à l’interphase sur des échantillons « bitume d’apport/bitume vieilli ». A l’interface, le temps d’étalement est influencé linéairement par la viscosité du liant vieilli. Concernant l’interphase, l’analyse des échantillons bitumineux a montré qu’une diminution de l’écart de températures entre les liants conduit à un meilleur mélange. Des méthodologies ont été développées pour suivre la migration du liant vieilli au moyen de techniques comme la micro fluorescence X, la microscopie infrarouge en mode ATR et en mode d’imagerie ATR. La microscopie infrarouge en mode d’imagerie ATR est particulièrement adaptée pour étudier la remobilisation du bitume vieilli à l’aide de la fonction carbonyle qui résulte de l’oxydation du bitume et traduit son état de vieillissement. Les résultats ont permis de déterminer les paramètres influents tels que la viscosité et la nature du liant vieilli ainsi que l’effet bénéfique d’un produit « régénérant » sur la remobilisation. L’effet d’une énergie d’agitation mécanique améliore également le mélange des liants. Concernant les résultats obtenus par micro fluorescence X, des éléments métalliques entrant dans la composition du bitume ont été choisis comme traceurs internes pour suivre la migration d’un liant. Des hypothèses ont été proposées pour expliquer les différences de migration des traceurs observées. Enfin, l’ensemble des méthodologies développées à l’échelle des liants a été appliqué à l’étude des produits routiers incorporant des granulats neufs et vieillis. Les résultats montrent une cohérence entre les tendances observées à l’échelle microscopique et macroscopique. Le procédé de fabrication à chaud favorise la remobilisation tandis que l’augmentation du taux d’agrégats d’enrobé le freine. L’augmentation du taux d’agrégats réduit également l’homogénéité du mélange bitumineux fabriqué qui a été évaluée au travers de la répartition spatiale de la fonction carbonyle, obtenue par un traitement statistique des cartographies chimiques par microscopie infrarouge. / In the road industry, the main challenge is to produce warm-mix asphalt mixtures while incorporating high rates of reclaimed asphalt, which come from the deconstruction of old pavement. However, the combination of recycling and the reduction of mix manufacture temperatures (warm mixes) raises technical issues about performance and durability of final pavement materials. In order to better predict final properties of these recycled materials, it is also necessary to understand phenomena occurring during the manufacture of recycled asphalt mixtures in the plant. The objectives of the PhD thesis are to understand and identify factors impacting wetting, remobilization and miscibility phenomena existing between organic and inorganic constituents of the bituminous mixture happening during the manufacturing step. The selected experimental approach consists in studying materials interactions according to a physicochemical approach at interfaces and interphases.Concerning wetting mechanisms at the “bitumen/aggregate” interface, some indicators were selected to assess wetting evolutions on a polished mineral slide. The binder ageing influence has also been studied. The bitumen viscosity and asphaltene content influence the wetting quality as well as the surface composition of the mineral substrate. Results have shown that “bitumen/aggregate” wetting evolutions were governed by a model associated to polished, porous and chemically heterogeneous surfaces.Remobilization of the aged binder (at a lower temperature) by the virgin one (heated at 160°C) has been studied at the interface and at the interphase of “aged binder/virgin binder “samples. At the bituminous interface, the spreading time is linearly influenced by the aged binder viscosity. At the bituminous interphase, bituminous sample analysis has shown that a reduction in the binders temperature difference leads to a better blend. Methodologies have been developed to monitor the aged binder migration using techniques such as X-ray micro fluorescence, infrared microscopy in ATR mode and in imaging ATR mode. Infrared microscopy in imaging ATR mode is a suitable technique to monitor the aged binder migration coupled to the carbonyl function marker resulting from the bitumen oxidation and ageing. Results have identified influent parameters corresponding to the aged binder viscosity and chemical composition, as well as the beneficial effect of a rejuvenator on remobilization. The effect of mechanical agitation energy also improves the binders blend. Concerning X-ray micro fluorescence results, binders remobilization has been assessed by the migration of metals which are involved in the bitumen internal composition. Some hypotheses have been proposed to explain observed migration differences of studied markers.Finally, all customized binder-scale methodologies have been applied to the study of road products incorporating virgin aggregates and reclaimed asphalt pavement. Results have shown similarities between observed trends at the microscopic and macroscopic scales. The hot manufacturing process promotes remobilization while the increase in the reclaimed asphalt rate limits it. The increase in the reclaimed asphalt rate also reduces the asphalt mixture homogeneity degree which has been evaluated through the carbonyl function spatial distribution, obtained by a chemical mappings statistical treatment.

Orientadores: Elizabete Jordão, Vanderley de Vasconcelos / Tese (doutorado) -U niversidade Estadual de Campinas, Faculdade de Engenharia Qimica / Made available in DSpace on 2018-08-15T22:04:22Z (GMT). No. of bitstreams: 1 Guzella_MarciaFlaviaRighi_D.pdf: 3799927 bytes, checksum: 15526a3c38edb5dad9d25ef7ffd6f1bb (MD5) Previous issue date: 2018-08-15T19:04:09Z / Resumo: O principal objetivo deste trabalho e o desenvolvimento de um processo para imobilização de rejeitos radioativos provenientes de usinas nucleares utilizando uma matriz de betume. Este processo visa a incorporação de rejeitos radioativos em betume para a obtenção de produtos de rejeito monolíticos, homogêneos, mecânica e quimicamente estáveis e com baixas taxas de lixiviação, propriedades importantes para aceitação destes produtos em depósitos de rejeitos. Foram avaliados dois betumes produzidos no Brasil, com pontos de amolecimento de 71,8 ºC e 91,3 ºC, respectivamente. O rejeito selecionado foi o concentrado de evaporador com as características dos rejeitos líquidos gerados em uma usina nuclear do tipo PWR. A escolha do rejeito foi feita em função do grande volume deste tipo gerado em usinas. Os dois betumes nacionais foram avaliados para evitar a importação da matriz de betume, inicialmente especificada para outras usinas nucleares da Europa que utilizam esta tecnologia. O equipamento utilizado para as incorporações foi o Sistema de Betuminização do CDTN, com porcentagens de rejeito incorporado variando de 30 a 40% em massa, valores estes compatíveis com os dados da literatura e da operação de usinas nucleares, que utilizam este processo para o tratamento dos rejeitos. Foram avaliados para o betume e para os produtos de rejeito as propriedades importantes para garantir tanto a operação segura do sistema e a segurança dos operadores, quanto a qualidade dos produtos obtidos, que são desenvolvidos para serem armazenados por longos períodos. As propriedades analisadas foram a penetração, o ponto de amolecimento, o ponto de fulgor, o teor de água e as taxas de lixiviação. A integridade e a durabilidade dos produtos de rejeito estão também relacionadas com as taxas de lixiviação dos constituintes do rejeito em água. Os procedimentos para determinar estas taxas estão estabelecidos em normas e a analise destes dados e utilizada para investigar os mecanismos de lixiviação (difusão, dissolução ou partição), permitindo prever a performance do produto e a modelagem deste ensaio. Esta avaliação deve ser feita antes da disposição final dos rejeitos e tem grande importância para a análise de segurança de repositórios. A pesquisa realizada contribuiu não apenas para o desenvolvimento do processo de incorporação de rejeitos em betume, mas também para as melhorias do Sistema de Betuminização do CDTN e para a implantação dos ensaios e métodos para as caracterizações necessárias. Concluiu-se que os betumes nacionais estudados podem ser usados para a imobilização de rejeitos das usinas nucleares brasileiras, pois foram obtidos produtos de rejeito com as propriedades requeridas para o armazenamento nos depósitos de rejeito. / Abstract: The main goal of this work is the development of a process to incorporate radioactive wastes from nuclear power plants into bitumen matrice. This process aims at obtaining waste forms that are monolithic, homogeneous and mechanical and chemically stable with low leaching rates. These features are important to evaluate the waste forms according to national and international standards. The obtained waste forms should meet the standard safety criteria for disposal in order to be accepted in a repository. Two Brazilian bitumens with softening point of 71,8 ºC and 91,3 ºC, respectively, were evaluated. The evaporator concentrate waste was selected to be used due to the large volume of this kind of waste generated in a PWR nuclear power plant. The two bitumens were evaluated so that the Brazilian material could be used to incorporate radioactive wastes thus avoiding the import of foreign raw material specified to other nuclear power plants in Europe, for instance. The immobilization campaigns were performed at the Bituminization Pilot Plant at CDTN and the incorporated waste concentrations ranged from 30 wt% to 40 wt%, which are in accordance with data from literature and also from plants that use the bituminization process. Important properties for bitumens and waste forms were evaluated in order to assure not only the system and occupational safety but also the quality of the waste forms which are developed to be stored for a long time in a repository. The analyzed properties are the penetration, the softening point, the flash point, the water content and the leaching rate. The integrity and durability of solid radioactive waste are also related to the waste constituents leaching rates in water. The procedure to determine such leaching rates are rule established and the analysis of these data is used to investigate the leaching mechanisms (diffusion, dissolution, partition) in order to determine the waste form performance and the experiment modeling. These analyses should be carried out before the waste form disposal and are important for safety assessment purposes. This research has also contributed not only to the development of the bituminization process to incorporate waste but also to the improvement of the Bituminization Pilot Plant at CDTN and to the implementation of methodologies and techniques to characterize bitumens and waste forms. This work concludes that is feasible to use the evaluated Brazilian bitumens for immobilization of nuclear power plants wastes in Brazil, obtaining waste forms with the required properties to be disposal in repository. / Doutorado / Sistemas de Processos Quimicos e Informatica / Doutor em Engenharia Química

Le bitume, fraction la plus lourde du pétrole brut, sert de liant de granulats dans la fabrication de revêtements routiers. Ce matériau complexe est particulièrement difficile à manipuler et à transporter du fait de sa viscosité très élevée à température ambiante. L’objectif de cette thèse a été de fabriquer une nouvelle classe de matériau, de la poudre de bitume, en couplant l’émulsification et la chimie sol-gel. En effet, des capsules organo-minérales composées d’un cœur de bitume et d’une écorce de silice ont été synthétisées à partir de deux types d’émulsions, les émulsions de Pickering ainsi que les émulsions dites « classiques »stabilisées par des tensioactifs et minéralisées par deux précurseurs de silice, un amorceur moléculaire pur, le TEOS, et une solution de silicate de sodium. Ce nouveau bitume, facilement manipulable, peut être stocké dans des conditions sévères de pression et de température et libère son cœur de bitume par association d’une action thermique et mécanique afin d’assurer ses fonctions d’enrobage. De plus, une étude du comportement interfacial bitume-phase aqueuse a été réalisée afin de proposer des hypothèses pour expliquer la stabilité fragile des émulsions de bitume que nous avons pu observer. / Bitumen, the heaviest fraction of crude oil plays the role of aggregate binder in road manufacturing. This complex material is very difficult to handle and transport due to its very high viscosity at room temperature. The aim of this PhD thesis was to elaborate a new class of material, bitumen powder, by coupling emulsion science and sol-gel chemistry. Indeed organo-mineral capsules made of a bitumen core anda silica shell have been synthesized from two types of emulsions: Pickering emulsions and "classical" emulsions i.e. surfactant-stabilized emulsions and using two silica precursors: the TEOS molecular initiator and sodium silicate solution. This new bitumen is easy to handle, can be stored in drastic pressure and temperature conditions while releasing the bitumen core under combination of heat and mechanical stirring to ensure aggregate coating. In addition a bitumen-water interface study has been performed in order to propose some hypotheses to explain the observed fragile stability of bitumen emulsions.

L'objectif de ce travail est de prédire le gonflement de fûts d'enrobés bitumineux contenant des déchets radioactifs en condition d'entreposage, de transport et de stockage. L'incorporation de radionucléides dans du bitume provoque en effet sa radiolyse et du dihydrogène est ainsi généré dans le matériau. Ce gaz est solubilisé dans la matrice jusqu'à ce que sa concentration atteigne une valeur limite, la saturation. Au-delà de celle-ci, un mécanisme de germination a lieu : des bulles sont formées. Elles vont par la suite croître grâce à l'apport de gaz par radiolyse et migrer sous l'effet de la poussée d'Archimède. Le gonflement du matériau résulte alors de la compétition entre création et évacuation de gaz. Un modèle a été construit pour décrire l'évolution d'une population de bulles. Sa résolution analytique n'étant pas possible, un code numérique a été développé. Les résultats montrent qu'une augmentation de la viscosité du fluide, du terme source de gaz apporté par radiolyse ou de la hauteur du récipient induisent une augmentation du gonflement et qu'une augmentation du coefficient de diffusion du gaz dans la matrice diminue le gonflement. Lorsque le fluide présente un seuil d'écoulement, le comportement de la population de bulles est modifié et l'évacuation de gaz par migration des bulles se fait par à-coups, contrairement au cas d'un fluide newtonien où une évacuation stationnaire est atteinte. Cette dernière a enfin servi à l'optimisation des conditions opératoires. / The aim of this PhD thesis is to predict the swelling of bitumen barrels in which radioactive salts are mixed. The bitumen exposed to radioactivity undergoes a chemical reaction: the radiolys. This implies a generation of dihydrogen. The created is solubilized until the concentration reaches a limit value which is called saturation. Over this limit nucleation of bubbles is observed. Then they will grow thank to the contribution of the gas generated by radiolys and they will be submitted to Archimede's principle so that they will rise in the fluid. The swelling is the result of the competition between generation and evacuation of gas. A model has been built to describe theevolution of a bubble population. Because of it is not possible to solve it analitically, a numerical program was developed. The results show that an increase of the fluid viscosity, the gas generation or the container height lead to an increase of the swelling and that an increase of the diffusioncoefficient contributes to a decrease of the swelling. In the particular case of a yield stress fluid, the behavior of the bubble population is modified and the evacuation of gas is done with several shots, at the opposite of the case of a Newtonian fluid for which a stationary evacuation is reached.

Asfaltsvägar har funnits och används i flera hundra år men tekniken man använde sig av förranvänds inte idag, utan den är utvecklats och blivit mer miljövänlig. Både vid tillverkningenav asfalten men också hur man lägger den. Idag är det både fler och tyngre fordon som kör påvägarna vilket leder till frågor kring asfaltens hållbarhet, hur företagen tänker kring miljön vidtillverkningen av asfalt, samt om det finns nya bättre tekniker som helt kan ersätta de gamla.Undersökningen är ämnad att jämföra hållbarheten mellan olika asfaltsbeläggningar pålågtrafikerande vägar, samt ta reda på vilket material som skiljer olika asfaltsmassorna åt.Frågan kommer att besvaras genom litteratur via internet samt genom intervjuer med olikaföretag i Örebro kommun.Undersökningen visade att det finns olika egenskaper som kännetecknar olikaasfaltsbeläggningar och beroende på vilka krav och förutsättningar en väg har, kommer enviss typ av beläggning att appliceras på just den vägen.En mjukgjord asfaltbetong är bra på en väg där flexibiliteten är ett krav, men denna typ avasfalt har en dålig miljöpåverkan eftersom man använder sig av fluxmedel, som är ettoljedestillerande produkt. Dock tillverkas dessa asfaltsmassor i en lägre temperatur och därföranvänds inte lika mycket energi och resurser på upphettningen, vilket man gör på en tätasfaltbetong då temperaturen bör vara kring 150 grader Celsius.PEAB och NCC sa att de använder sig av bio olja eller neutralt koldioxidbränsle vidtillverkningen av varmtillverkade asfaltsmassor för att minska miljöpåverkan. Ett annat sättatt för företagen att tänka på miljön är att återanvända gammal asfalt.Bitumen är ett bindemedel som används när man blandar asfalten, upphettningen av bitumenär dock skadligt för miljön. Det finns ett miljövänligare alternativ som heter lignin och somman tror kan likställas med bitumen, men detta är inte är aktuellt i dagsläget. Delvis för att detinte är testat på bilvägar än men också för att man använt sig av bitumen en längre tid ochföretagen känner sig säkra med egenskaperna och hållbarheten. Tills man testat ligninet ochvet att det är hållbart har man istället gjort andra små förändringar för att tänka på miljön, somtill exempel att transportera asfalten i ekovänliga fordon. Trafikverket har tillsammans medNCC utvecklat verktyg som heter EKA, som ska kontrollera koldioxidutsläppen vidtillverkningen.Sammanfattningsvis så skiljer sig olika asfaltsbeläggningar från varandra, vilket är positivt dåde ställs olika krav på vägarna beroende på vart de ska användas, så det finns olika alternativatt välja mellan. Företagen har miljön i åtanke vid asfaltstillverkningen även fast det ännu inteär aktuellt att ersätta bitumen med något annat medel. De har vidtagits andra åtgärder för attminska miljöpåverkan så som att använda sig av bensinsnålare fordon samt använda deverktyg som ska kontrollera koldioxidutsläppen. / Asphalt roads have been around and used for hundreds of years, but the technology used atthat time is no longer relevant and used today, but it has been developed and become moreenvironmentally friendly. Both in the manufacture of the asphalt but also how to lay it. Today,there are both more and heavier vehicles driving on the roads, which leads to questions aboutthe sustainability of asphalt, how companies think about the environment in the production ofasphalt, and whether there are new, better technologies that can completely replace the oldones.The study is intended to compare the durability of different asphalt coatings on low-trafficroads and to find out how the material in these asphalt coatings differentiates from one andanother. The question will be answered through literature via the Internet and throughinterviews with various companies in the municipality of Örebro.The study showed that different qualities characterize different asphalt coatings anddepending on the requirements and conditions a road has, a certain type of coating will beapplied to that road. Softened asphalt concrete is good on a road where flexibility is arequirement, but this type of asphalt has a bad environmental impact because of the use offlux oil, which is an oil distilling product. However, these asphalt masses are produced at alower temperature and therefore less energy and resources are used during the heating, incomparison to a dense asphalt concrete where the temperature should be around 150 degreesCelsius when heating up. PEAB and NCC said they use bio-oil or neutral carbon dioxide fuelin the production of hot-made asphalt pulp to reduce environmental impact. Another way forcompanies to think about the environment is to reuse old asphalt.Bitumen is a binder used when mixing the asphalt, but the heating of bitumen is harmful tothe environment. There is a more environmentally friendly alternative called lignin, whichbeliefs can be compared with bitumen, but this is not currently used today. Partly because ithas not been tested on car roads yet but also because bitumen has been used for a long timeand companies feel secure with the quality and durability of bitumen. Until lignin has beentested on roads and knows that it is durable, there have been other small changes instead tothink about the environment, such as transporting the asphalt in eco-friendly vehicles.Together with NCC and the Swedish Transport Administration, they have developed a toolcalled EKA, which will control carbon dioxide emissions during manufacture.In summary, different asphalt coatings differ from one another, which is a positive thing whenthere are different requirements on the roads depending on where they are to be used, so thereare different alternatives to choose from. The companies have the environment in mind whenmaking asphalt, although it is not yet relevant to replace bitumen with any other means. Theyhave taken other measures to reduce the environmental impact, such as using environmentallyfriendly vehicles and using the tools to control carbon dioxide emissions.

Dwindling conventional oil resources has caused exploration efforts to focus elsewhere. Bitumen from oil sands has emerged as one of the primary unconventional oil resources in use today. Quadrise Canada Corporation has harnessed this unconventional oil by developing their bitumen-in-water emulsion known as MSAR (Multi-Phase Superfine Atomized Residue). Fuel-in-water emulsions are linked to a combustion phenomenon known as micro-explosion, which are associated with an increase in combustion efficiency and decrease in harmful emissions. A study has been conducted of the MSAR fuel to help advance the optimization and modeling of its use in spray combustors so as to best harness the potential. Quantitative and qualitative data has been obtained during combustion experiments of the fuel that will attribute to this end. Additionally, a simplified statistical model is presented based on the governing equations to describe the atomization that occur as a result of micro-explosions of the MSAR fuel as well as a simple model to represent internal force needed for a micro-explosion to occur. The results of this study continue to reinforce the understanding that micro-explosions cannot be attributed to one overriding physical principal, but rather are th result from variations in turbulent, dynamic, and thermal forces.

This work deals with the study of organic matter in the South Moravian lignite using the available physico-chemical methods and the results obtained are eventually considered for non-energy applications of lignite. Lignite organic matter was studied by degradation methods, which included CuO oxidation, thermochemolysis with TMAH and DFRC method. Special attention was paid to the lignite oxidation with hydrogen peroxide, which was carried out under different reaction conditions (time and temperature). Thermal degradation was performed in an inert atmosphere in order to observation of chemical change of lignite (including lignite after extraction with chloroform, demineralised lignite, remineralised lignete) during pyrolysis by means of various methods, especially TG-FTIR for analysis of gaseous products and FTIR for analysis the residual lignite after pyrolysis. Further, water-soluble fractions from lignite were characterized, particularly in terms of the content of organic substances.