Hydrocracking and hydrotreating are bitumen upgrading technologies designed to enhance fuel quality by decreasing its density, viscosity, boiling point and heteroatom content via hydrogen addition. The aim of this thesis is to model and simulate an upgrading and integrated gasification combined cycle then to evaluate the feasibility of integrating slurry hydrocracking, trickle-bed hydrotreating and residue gasification using the Aspen HYSYS® simulation software. The close-coupling of the bitumen upgrading facilities with gasification should lead to a hydrogen, steam and power self-sufficient upgrading facility with CO2 capture. Hydrocracker residue is first withdrawn from a 100,000 BPD Athabasca bitumen upgrading facility, characterized via ultimate analysis and then fed to a gasification unit where it produces hydrogen that is partially recycled to the hydrocracker and hydrotreaters and partially burned for power production in a high hydrogen combined cycle unit. The integrated design is simulated for a base case of 90% carbon capture utilizing a monoethanolamine (MEA) solvent, and compared to 65% and no carbon capture scenarios. The hydrogen production of the gasification process is evaluated in terms of hydrocracker residue and auxiliary petroleum coke feeds. The power production is determined for various carbon capture cases and for an optimal hydrocracking operation. Hence, the feasibility of the integration of the upgrading process and the IGCC resides in meeting the hydrogen demand of the upgrading facility while producing enough steam and electricity for a power and energy self-sufficient operation, regardless of the extent of carbon capture.

El aumento de la cantidad de lodos y las dificultades inherentes a su aplicación agrícola y/o disposición en vertederos, hace necesario encontrar nuevas alternativas para su gestión. A nivel europeo, hoy en día se tiende hacia la aplicación de tratamientos térmicos (incineración, pirólisis y gasificación) que permiten una valoración energética de los lodos, si bien generan un residuo sólido que sigue siendo necesario gestionar. El problema medioambiental provocado por (malos) olores resulta difícil de abordar de una manera genérica, teniendo en consideración la propia naturaleza del olor y sus posibles causas. Los olores en las EDARs son provocados básicamente por la degradación de la materia orgánica en condiciones anaeróbicas y se detectan en todas las operaciones unitarias en diferentes niveles de concentración. Esta tesis incidiendo en ambos aspectos, tiene por objeto investigar la valorización de lodos como materiales precursores de adsorbentes/ catalizadores para la eliminación de olores en el entorno de las EDARs, maximizando la reutilización de los lodos.Para la realización de los experimentos se han seleccionado lodos procedentes de tres EDARs situadas en la región de Girona (SC, SB, SL) que difieren en cuanto al tratamiento de los lodos. Ambas muestras han sido caracterizadas con el fin de determinar las diferencias más importantes en los lodos de partida. Los parámetros de caracterización incluyen el análisis de composición química (análisis elemental e inmediato, determinación contenido en cenizas, medida pH, DRX, FT-IR, SEM / EDX) así como análisis de superficie (adsorción de N2 y CO2). En primer lugar los lodos caracterizados han sido sometidos a diferentes tratamientos térmicos de gasificación y pirólisis y los adsorbentes/ catalizadores obtenidos se han probado como adsorbentes para la eliminación de H2S. Como consecuencia de este estudio, se ha desechado el uso de uno de lodos (SC) puesto que se obtenían resultados muy similares a (SB), a continuación el estudio se centró en el lodo de SL. Con este objetivo se han preparado 12 muestras 6 de ellas pirolizadas y 6 gasificadas en el rango de temperaturas que comprende 600-1100 ºC. Posteriormente las muestras han sido caracterizadas y se ha determinado la capacidad de eliminación (x/M) del H2S. Los resultados muestran que hemos sido capaces de obtener unos materiales que si bien, presentan un bajo desarrollo de porosidad dan lugar a valores de capacidades de eliminación elevados y comparables a carbones y materiales adsorbentes comerciales (Centaur, Sorbalit). Las elevadas eficiencias de eliminación se atribuyen básicamente a la presencia de especies catalíticamente activas tales como los óxidos mixtos de calcio y hierro determinados por DRX en las muestras tratadas térmicamente. El segundo bloque de resultados se centra la mejora de las propiedades texturales de estos materiales adsorbentes. Con este objetivo se llevaron acabo procesos de activación física con CO2 y química con H3PO4 e hidróxidos alcalinos (NaOH y KOH), que hasta el momento no se había probado con este tipo de precursores. Los resultados indican que la activación física (CO2) y química (H3PO4) no son unos buenos métodos para la obtención de adsorbentes altamente porosos con este tipo de materia prima bajo las condiciones probadas, sin embargo la activación con hidróxidos alcalinos da lugar a materiales adsorbentes con superficies específicas de hasta 1600 m2g-1. En el caso de la activación con hidróxidos, tanto el incremento de la relación agente activante/ precursor como el incremento de la temperatura producen un descenso del rendimiento, al mismo tiempo que incrementan el valor de SBET.Los materiales resultantes de la activación con hidróxidos alcalinos se han probado como adsorbentes/ catalizadores para la eliminación de H2S. Los resultados indican que un incremento del área superficial no es indicativo de un aumento de la capacidad de eliminación dada la naturaleza ácida de estos materiales obtenidos. Con el fin de contrarrestar el efecto ácido de estos materiales se han realizado los mismos ensayos añadiendo NaOH al lecho de reacción llegando a valores de x/M de hasta 450 mgg-1. Posteriormente también se han realizado ensayos de eliminación de NH3 con algunas de estas muestras, y los resultados obtenidos de x/M son del orden de carbones activados comerciales. Los materiales adsorbentes obtenidos tras la activación con hidróxidos alcalinos se convierten en materiales muy atractivos para ser utilizados como adsorbentes/ catalizadores de múltiples contaminantes (COVs, Hg...). / During the last years there has been an increase in the number of wastewater treatment plants arising after the implementation of regulatory policies focused on sustainable development of contemporary societies. A large quantity of sewage sludge is produced and in addition, some traditional disposal routes are coming under pressure and others are being phased out. Therefore, it is necessary to seek cost-effective and innovate solutions to the problem incurred by sewage sludge disposal. Nowadays, the tendency in Europe is to use this residue to obtain energy by thermal treatments, such as incineration, pyrolysis and gasification, though during this treatment a residue that needs to be disposed is generated.Furthermore, the environmental problems prompted by odors are difficult to solve take considering the different origin and reasons for these bad smells. Bad smell in waste water treatment plants is produced basically by organic matter degradation. This thesis takes into account these two aspects. The aim of this work focuses on the revalorization of sewage sludge to obtain / prepare adsorbents / catalysts from various sewage-based precursors and their application in H2S and in NH3 abatement at ambient temperature. These two latter compounds are paradigmatic in odor related problems.The sewage sludge samples used in this study were obtained from three Spanish WWTPs located in Girona (SC, SB, SL). The influent of these selected facilities is mainly of domestic origin and differs in sludge treatment schemes. A detailed characterization of the solids under consideration is carried out, as a purpose to define the main differences. The techniques used to characterize precursors include chemical characterization (elemental analysis, ash content, pH determination, DRX, FT-IR, SEM / EDX), as well as their porosity characterization (physical adsorption of N2 and CO2).In the first part of the study we focused on dried samples that were subjected to different thermal treatments such as pyrolysis and gasification at different temperatures. The adsorbents/catalysts obtained were used for H2S removal. Afterwards, 12 samples were prepared from SL, 6 of them gasified between 600 - 1100 ºC and 6 pyrolysed at the same temperatures. The samples were characterized and used as an adsorbents for H2S removal. The results shown that we were able to obtain adsorbents with high removal efficiencies despite their low porosity development. These adsorption capacities values (x/M) are in the same range or even higher than x/M values from commercial active carbons (Centaur, Sorbalit). These high x/M values have been prompted to catalytic species such as dicalcium ferrite, identified by XRD.The second part of the study was focused on the preparation of adsorbents from these sewage sludge-based precursors (SB, SL) using different activation processes. Specifically, physical activation with CO2, H3PO4 activation and alkaline hydroxide activation were explored. It is worth noticing that, as far as we know, there are no previous studies in the literature dealing with the activation of sewage sludge by alkaline hydroxides (NaOH or KOH), whereas CO2 and H3PO4 have been scarcely used for the activation of this precursor. The results of the textural characterization of the materials prepared from physical activation by CO2 and chemical activation by H3PO4 show that, these precursors are not a suitable for the preparation of adsorbents by these two methods. Nevertheless, chemical activation by alkaline hydroxides can be a suitable method to develop porosity and surface areas higher than 1600 m2g-1 can be obtained from both sewage sludge precursors (SB, SL). An increase in the hydroxide: precursor ratio leads to an enhancement of the adsorption capacity of the adsorbents. The resultant materials were tested as adsorbents/catalyst for H2S abatement. The results shown that we are been able to obtain adsorbents from sludge-based materials with high surface areas but with relatively low adsorption capacities as a consequence of its acidic nature. NaOH was added to the adsorption bed to counteract the acidic nature of these materials. The x/M values obtained are higher than 450 mgg-1. In addition, some of these materials were used for NH3 removal being the results obtained comparable to those for commercial activated carbons x/M values, tested under similar experimental conditions. These "new" activated materials can be used as adsorbents for many environmental applications such as VOC, Hg removal, etc.

Questions that were answered in the dissertation: Which process is suitable to desulphurize biogas knowing that chemical absorption will be used to separate CO2? Which absorption solvent is suitable to separate CO2 from concentrated gases such as biogas at atmospheric pressure? What properties of the selected solvent, namely aqueous diglycolamine (DGA), are already known? How to determine solvent properties such as equilibrium CO2 solubility under absorption and desorption conditions using simple, but robust apparatuses? What values do solvent properties such as density, viscosity and surface tension take at various DGA contents and CO2 loadings? How do primary alkanolamine content and CO2 loading influence solvent properties? What is the optimal DGA content in the solvent? What is the optimal desorption temperature at atmospheric pressure? How can equilibrium CO2 solubility in aqueous DGA solvents be simulated? What is the uncertainty in the results? How to debottleneck an absorber and increase its gas-treating capacity? How to determine the optimal lean loading of the absorption solvent? What are the characteristics of the absorption process that uses aqueous DGA as the solvent to separate CO2 from biogas and is more energy efficient and safer than the state-of-the-art processes? How to quantitatively compare the hazards of absorption solvents? What is the disposition of the German population towards hazards from biogas plants? What are the favourable and adverse environmental impacts of biomethane? / Fragen, die in der Dissertation beantwortet wurden: Welches Verfahren ist zur Entschwefelung von Biogas geeignet, wenn die chemische Absorption zur CO2-Abtrennung genutzt wird? Welches Absorptionsmittel ist geeignet, um CO2 aus konzentrierten Gasen, wie Biogas, bei atmosphärischem Druck abzutrennen? Welche Eigenschaften des ausgewählten Absorptionsmittels, wässriges Diglykolamin (DGA), sind bereits bekannt? Wie wird die CO2-Gleichgewichtsbeladung unter Absorptions- und Desorptionsbedingungen mit einfachen und robusten Laborapparaten bestimmt? Welche Werte nehmen die Absorptionsmitteleigenschaften wie Dichte, Viskosität und Oberflächenspannung bei verschiedenen DGA-Gehalten und CO2-Beladungen? Wie werden die Absorptionsmitteleigenschaften durch den Primäramin-Gehalt und die CO2-Beladung beeinflusst? Was ist der optimale DGA-Gehalt im Absorptionsmittel? Was ist die optimale Desorptionstemperatur bei atmosphärischem Druck? Wie wird die CO2-Gleichgewichtsbeladung im wässrigen DGA simuliert? Welche Ungenauigkeit ist zu erwarten? Wie wird eine Absorptionskolonne umgerüstet, um die Kapazität zu erweitern? Wie wird die optimale CO2-Beladung des Absorptionsmittels am Absorbereintritt (im unbeladenen Absorptionsmittel) bestimmt? Was sind die Prozesseigenschaften eines Absorptionsverfahrens, das wässriges DGA als Absorptionsmittel nutzt sowie energieeffizienter und sicherer als Verfahren auf dem Stand der Technik ist? Wie kann das Gefahrenpotenzial von Absorptionsmittel quantitativ verglichen werden? Wie werden Gefahren aus einer Biogasanlage durch die deutsche Bevölkerung wahrgenommen? Welche positive und negative Umweltauswirkung hat Biomethan?

Hydrocracking and hydrotreating are bitumen upgrading technologies designed to enhance fuel quality by decreasing its density, viscosity, boiling point and heteroatom content via hydrogen addition. The aim of this thesis is to model and simulate an upgrading and integrated gasification combined cycle then to evaluate the feasibility of integrating slurry hydrocracking, trickle-bed hydrotreating and residue gasification using the Aspen HYSYS® simulation software. The close-coupling of the bitumen upgrading facilities with gasification should lead to a hydrogen, steam and power self-sufficient upgrading facility with CO2 capture. Hydrocracker residue is first withdrawn from a 100,000 BPD Athabasca bitumen upgrading facility, characterized via ultimate analysis and then fed to a gasification unit where it produces hydrogen that is partially recycled to the hydrocracker and hydrotreaters and partially burned for power production in a high hydrogen combined cycle unit. The integrated design is simulated for a base case of 90% carbon capture utilizing a monoethanolamine (MEA) solvent, and compared to 65% and no carbon capture scenarios. The hydrogen production of the gasification process is evaluated in terms of hydrocracker residue and auxiliary petroleum coke feeds. The power production is determined for various carbon capture cases and for an optimal hydrocracking operation. Hence, the feasibility of the integration of the upgrading process and the IGCC resides in meeting the hydrogen demand of the upgrading facility while producing enough steam and electricity for a power and energy self-sufficient operation, regardless of the extent of carbon capture.

Questions that were answered in the dissertation: Which process is suitable to desulphurize biogas knowing that chemical absorption will be used to separate CO2? Which absorption solvent is suitable to separate CO2 from concentrated gases such as biogas at atmospheric pressure? What properties of the selected solvent, namely aqueous diglycolamine (DGA), are already known? How to determine solvent properties such as equilibrium CO2 solubility under absorption and desorption conditions using simple, but robust apparatuses? What values do solvent properties such as density, viscosity and surface tension take at various DGA contents and CO2 loadings? How do primary alkanolamine content and CO2 loading influence solvent properties? What is the optimal DGA content in the solvent? What is the optimal desorption temperature at atmospheric pressure? How can equilibrium CO2 solubility in aqueous DGA solvents be simulated? What is the uncertainty in the results? How to debottleneck an absorber and increase its gas-treating capacity? How to determine the optimal lean loading of the absorption solvent? What are the characteristics of the absorption process that uses aqueous DGA as the solvent to separate CO2 from biogas and is more energy efficient and safer than the state-of-the-art processes? How to quantitatively compare the hazards of absorption solvents? What is the disposition of the German population towards hazards from biogas plants? What are the favourable and adverse environmental impacts of biomethane? / Fragen, die in der Dissertation beantwortet wurden: Welches Verfahren ist zur Entschwefelung von Biogas geeignet, wenn die chemische Absorption zur CO2-Abtrennung genutzt wird? Welches Absorptionsmittel ist geeignet, um CO2 aus konzentrierten Gasen, wie Biogas, bei atmosphärischem Druck abzutrennen? Welche Eigenschaften des ausgewählten Absorptionsmittels, wässriges Diglykolamin (DGA), sind bereits bekannt? Wie wird die CO2-Gleichgewichtsbeladung unter Absorptions- und Desorptionsbedingungen mit einfachen und robusten Laborapparaten bestimmt? Welche Werte nehmen die Absorptionsmitteleigenschaften wie Dichte, Viskosität und Oberflächenspannung bei verschiedenen DGA-Gehalten und CO2-Beladungen? Wie werden die Absorptionsmitteleigenschaften durch den Primäramin-Gehalt und die CO2-Beladung beeinflusst? Was ist der optimale DGA-Gehalt im Absorptionsmittel? Was ist die optimale Desorptionstemperatur bei atmosphärischem Druck? Wie wird die CO2-Gleichgewichtsbeladung im wässrigen DGA simuliert? Welche Ungenauigkeit ist zu erwarten? Wie wird eine Absorptionskolonne umgerüstet, um die Kapazität zu erweitern? Wie wird die optimale CO2-Beladung des Absorptionsmittels am Absorbereintritt (im unbeladenen Absorptionsmittel) bestimmt? Was sind die Prozesseigenschaften eines Absorptionsverfahrens, das wässriges DGA als Absorptionsmittel nutzt sowie energieeffizienter und sicherer als Verfahren auf dem Stand der Technik ist? Wie kann das Gefahrenpotenzial von Absorptionsmittel quantitativ verglichen werden? Wie werden Gefahren aus einer Biogasanlage durch die deutsche Bevölkerung wahrgenommen? Welche positive und negative Umweltauswirkung hat Biomethan?

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