Adsorption in porous materials is a promising technology for CO2 capture and storage. Particularly important applications are adsorption separation of streams associated with the fossil fuel power plants operation, as well as natural gas sweetening. High surface area activated carbons are a promising family of materials for these applications, especially in the high pressure regimes. As the streams under consideration are generally multi-component mixtures, development and optimization of adsorption processes for their separation would substantially benefit from predictive simulation models. In this project we combine experimental data and molecular simulations to systematically develop a model for a high surface area carbon material, taking activated carbon Maxsorb MSC-30 as a reference. Our study starts from the application of the well-established slit pore model, and then evolves through the development of a more realistic model, based on a random packing of small graphitic fragments. In the construction of the model, we introduce a number of constraints, such as the value of the accessible surface area, concentration of the surface groups and pore volume, to bring the properties of the model structure close to the reference porous material. Once a plausible model is developed, its properties are further tuned through comparison between simulated and experimental results for carbon dioxide and methane. The model is then validated by predictions for the same species at different conditions and by prediction of other species involved in the carbon capture processes. The model is applied to simulate the separations involved in pre and post combustion capture processes and sweetening of sour natural gas, using realistic conditions and compositions for the multicomponent mixtures. Finally, it is used to explore the effect of water in pre and post combustion separations.

Le but principal de ce projet doctoral est de déterminer le potentiel d'amélioration de l'efficacité énergétique du système de captage de carbone dans les stations thermiques de production d'électricité, par l'intégration optimale des éjecteurs monophasiques. Il s'agit du système de captage postcombustion du dioxyde de carbone (CO2) par absorption/désorption utilisant la monoéthanolamine (MEA). Les éjecteurs intégrés utilisent des rejets thermiques de 100 °C qu'on retrouve dans les stations thermiques de production d'électricité. La revalorisation de ces rejets permet la substitution partielle de vapeur de turbine à coût élevé, qui serait autrement prise de la centrale thermique. Le deuxième objectif de la thèse est d'évaluer expérimentalement la performance d'un éjecteur à vapeur où le fluide secondaire de l'éjecteur est un mélange de vapeur d'eau et d'un gaz non-condensable, dans le cas présent, le CO2. Deux tuyères d'éjecteur à vapeur, d'un diamètre de 4.60 mm et 4.23 mm, ont été évaluées sur une plage de niveaux de CO2 dans le fluide secondaire, jusqu'à environ 40% en masse. La pression primaire était maintenue à 450 kPa avec une surchauffe à 10 °C et la pression secondaire était de 70 kPa. On a constaté que la pression critique ne changeait pas à mesure que la fraction massique de CO2 dans le fluide secondaire augmentait. Cependant, le rapport d'entraînement a augmenté de façon linéaire sur la plage expérimentale. Une amélioration de 23% du rapport d'entraînement par rapport à la vapeur pure a été observée lorsque le fluide secondaire contient 42% de CO2 par masse. Ce comportement contraste nettement avec le comportement observé expérimentalement d'un éjecteur à vapeur pure, où une augmentation du rapport d'entraînement se produit au détriment d'une diminution de la pression critique. Trois articles détaillés ont été publiés sur divers scénarios d'intégration d'un éjecteur à vapeur dans un procédé de captage d'absorption/désorption. Le solvant de référence était de 20% en masse de monoéthanolamine (MEA). Trois configurations principales ont été étudiées, selon le choix du fluide utilisé pour produire la vapeur secondaire : éjecteur sur condensat, éjecteur sur pauvre ou éjecteur sur riche. La première publication de revue scientifique a porté sur le procédé de désorption et a présenté une méthode de raccourci basée sur les propriétés du mélange CO2-MEA-H2O à l'équilibre. Les simulations ont révélé des réductions dans la quantité requise d'énergie de haute qualité, de 10 à 25%. Un simulateur de procédé commercial, Aspen Plus, a été utilisé pour les deux autres publications. Dans la deuxième publication de revue scientifique, le module cinétique rate-based a été utilisé, au lieu du module d'équilibre, pour la modélisation de l'absorbeur et du désorbeur, permettant des évaluations énergétiques plus près des valeurs qu'on retrouve dans la littérature courante. Une étude a été réalisée pour comparer un scénario de préchauffage de la vapeur primaire par des rejets thermiques externes avec un scénario d'intégration de la chaleur interne. Cette deuxième publication a montré des économies d'énergie de haute qualité, de 10 à 14%, les scénarios avantageux ayant été «éjecteur sur condensat» et «éjecteur sur pauvre». / Abstract : The main goal of the doctoral project is to determine to what extent the optimal integration of single-phase ejectors might reduce the large amount of energy required to capture carbon dioxide from electric power generation facilities. More specifically, the objective is to determine if ejectors can be advantageously integrated into a post-combustion absorption/desorption carbon dioxide (CO2) capture process using monoethanolamine (MEA). The integrated ejectors will use waste heat of 100 °C from the electric power plant. The upgraded waste heat can partially replace valuable turbine steam that would otherwise be taken from the power plant. The second objective of the thesis is to experimentally evaluate the performance of a steam ejector where the ejector secondary fluid is a mixture of steam and a non-condensable gas, in this case CO2. Two steam ejector nozzles, of 4.60 mm and 4.23 mm diameter, were evaluated over a range of secondary fluid CO2 levels, up to 42% by mass. The primary pressure was maintained at 450 kPa with 10 °C superheat and the secondary pressure was 70 kPa. It was found that the critical exit pressure did not change as the mass fraction of CO2 in the secondary fluid increased. The entrainment ratio, however, increased approximately linearly over the experimental range. An improvement of 23% in the entrainment ratio, as compared with pure steam, was found when the secondary fluid contains 42% CO2 by mass. This behaviour is in sharp contrast to the experimentally observed behaviour of a pure steam ejector, where an increase in entrainment ratio comes at the expense of a decrease in the ejector exit critical pressure. Three published papers investigated various scenarios for the integration of a steam injector into an absorption/desorption post-combustion capture process. The reference solvent was 20% weight monoethanolamine (MEA). Three principal configurations were studied, according to the choice for the liquid flow used to produce the ejector secondary steam: ejector on condensate, ejector on lean or ejector on rich. The first journal publication focused on the desorption process and presented a shortcut method based on CO2-MEA-H2O equilibrium vapour liquid data. The simulations revealed reductions in the required amount of valuable energy from 10 to 25%. A commercial process simulator, Aspen Plus, was used for two other publications. In the second journal publication, the kinetic rate-based module was employed to model the absorber and desorber, providing energy evaluations closer to values in the open literature. A study was included comparing preheating the primary steam with waste heat or by heat integration. The rate-based simulation found valuable energy savings of 10 to 14%, with the "ejector on condensate" and "ejector on lean" again being the advantageous scenarios.

The separation of industrially important gases into pure supplies that can be used for many practical applications is based mainly on energy intensive methods such as the cryogenic distillation which is costly and energy intensive. Therefore other routes have been introduced to industrial separation of gases such as the selective adsorption using porous solid materials. Zeolites and activated carbon are the most widely used recyclable energy-efficient porous solid materials for industrial gas separations, however the low uptake and selectivity hurdles their commercialization in some separation applications. Metal organic frameworks (MOFs) have been extensively studied as solid porous materials in term of gas separations nevertheless the future of MOFs for practical gas separations is considered to be vague and stringent due to their low stability, low capacity and selectivity especially at low partial pressures of the adsorbed gas, the competitive adsorption of the contaminants such as H2O, NOX and SOX, high cost of the organic ligands, besides the challenges of the formulation of MOFs which is very important in the MOFs marketing. In this context we present new porous materials based on inorganic linkers as well as the organic molecules, Organic-Inorganic Hybrid Materials, which were found to conquer the current challenges for the exploitation of MOFs in practical gas separation such as separation of trace and low CO2 concentrations and Xe separation from Xe/Kr mixtures. The work presented herein encompasses the development of novel 48.67 topology metal organic material (MOM) platform of formula [M(bp)2(M'O4)] (M= Co or Ni; bpe= bipyridine-type linkers; M'= W, Mo or Cr) that have been assigned RCSR code mmo based upon pillaring of [M(bp)2] square grids by angular WO42-, MoO42- or CrO42- pillars. Such pillars are unexplored in MOMs. They represent ideal platforms to test the effect of pore size and chemistry upon gas sorption behavior since they are readily fine-tuned and can be varied at their 3-positions (metal, organic linker and the inorganic pillar) without changing the overall structure. Such an approach allows for systematic control of pore size to optimize interactions between the framework and the adsorbent in order to enhance selectivity and/or gas uptake. Interestingly, these nets showed a high chemical stability in air, water, boiling water and in a wide range of pH which is certainly a desirable property in industry and commercialization of MOMs. [Ni(bpe)2(MoO4)] (bpe= 1,2-bis(4-pyridyl) ethane), MOOFOUR-1-Ni, and its chromate analog, CROFOUR-1-Ni, exhibit remarkable CO2 affinity and selectivity, especially at low loading. This behavior can be attributed to exceptionally high isosteric heats of adsorption (Qst) of CO2 in MOOFOUR-1-Ni and CROFOUR-1-Ni of ~56 and ~50 kJ/mol, respectively, at zero loading. These results were validated by modeling which indicate that the electrostatics of such inorganic anions towards CO2 affords favourable attractions to CO2 that are comparable to the effect of unsaturated metal centres. The use of WO42- instead of CrO42- or MoO42- as an angular pillar in mmo topology nets has afforded two isostructural porous nets of formula [M(bpe)2WO4] (M = Co or Ni, bpe=1,2-(4-pyridyl)ethene). The Ni variant, WOFOUR-1-Ni, is highly selective towards CO2 thanks to its exceptionally high isosteric heat of adsorption (Qst) of -65.5 kJ/mol at zero loading. The fine-tunability and the inherent modularity of this platform allow us exquisite design and control over the pore chemistry through the incorporation of different functionalities inside the channels of the networks which was then demonstrated as valuable strategy in terms of carbon dioxide capture at condition relevant to the direct CO2 capture from air. The exploitation of 4,4'-azopyridine in the design and synthesis of CROFOUR-2-Ni, an isostructure of CROFOUR-1-Ni, affords a paradigm shift in the CO2 adsorption properties as exemplified by the enhanced CO2 isosteric heat of adsorption at moderate and high loading in CROFOUR-2-Ni and the superior CO2 selectivity even for trace and low CO2 concentration. The two isostructures, CROFOUR-1-Ni and CROFOUR-2-Ni have been also investigated in term of Xe adsorption and separation from Xe/Kr mixtures. The two structures were found to exhibit the remarkable Xe affinity and selectivity which, together with high stability, good recyclability, low regeneration energy and low cost of the two materials could not only diminish the cost of the Xe and Kr production but also can potentially afford a high purity of the separated gases.

Les polymères conducteurs organiques présentent des propriétés électriques qui offrent de nombreuses possibilités de materiaux, tels que les batteries, les diodes électroluminescentes, les dispositifs microélectroniques, les cellules photovoltaïques, les inhibiteurs de corrosion, les capteurs, etc. Parmi eux, la PANI et le PPS ont été largement étudiés en raison de leur stabilité ou propriétés électriques de protonation réglable ainsi que leur faible coût de production. Néanmoins, ces structures sont généralement représentées comme des structures linéaires et donc il y a un intérêt à obtenir des structures hémicyclique ou des analogues cycliques pour augmenter leur potentiel d'utilisation comme agents de séquestration de métaux et/ou de gaz, matériaux de détection ainsi que des nouveaux semi-conducteurs organiques cycliques qui présentent des propriétés différentes de leurs homologues linéaires. Avec la croissance démographique et l'industrialisation, la consommation d'énergie est en nette progression ce qui entraîne la libération de grandes quantités de CO2 dans l'atmosphère et perturbe l'équilibre en carbone de notre planète. Une option pour réduire la concentration de CO2 est l'utilisation de la capture du CO2 et de la technologie de stockage. Dans ce contexte, nous démontrons ici une stratégie basée sur une réaction de substitution nucléophile aromatique, pour la synthèse de hétéracalixarenes qui sont des précurseurs de calixarènes avec un hétéroatome sur le pont, leurs intermédiaires et les structures oligomèriques sont dérivés de ces hétéracalixarenes avec un sélectivité, des propriétés de capture et optoéletroniques optimisées pour un utilisation en capture de CO2. / Optoelectronic properties of π-conjugated chromophores have been widely used since the discovery in the late 70’s of the conducting properties of synthetic organic polymers. Indeed, due to their chemical structures organic conducting polymers exhibit electrical properties that provide useful materials such as batteries, light-emitting diodes, microelectronic devices, photovoltaic cells, corrosion inhibitors, sensors etc. Among them, polyaniline and polysulfide have been extensively studied for this purpose due to their environmental stability, oxidation or protonation-adjustable electrical properties and low cost production. Nevertheless, these structures are generally depicted as linear structures and there is an interest in achieving hemicyclic or cyclic analogues structures to extend their potential of use as metal-gas sequestering agents and/or sensing materials as well as new organic cyclic semiconductors exhibiting different properties from their linear counterparts. With population growth and increased industrialization in the world, energy consumption is increasing significantly resulting in the release of large amounts of carbon dioxide (CO2) into the atmosphere and disturbing the carbon balance of our planet. One way to reduce the CO2 concentration is the use of carbon capture and storage technology. In this context, we report here a very simple strategy, based on a nucleophilic aromatic substitution reaction, for the synthesis of heteracalixarenes, their intermediates and oligomeric structures derived from these heteracalixarenes with optimized optoelectronic properties, selectivity and capture properties for use in carbon capture.

Le captage de polluants des effluents industriels, et plus particulièrement du CO2, est un défi majeur à relever. Le procédé de captage du CO2 basé sur l’absorption par des solutions aqueuses d’amines est la technique la plus maîtrisée pour le traitement des fumées en postcombustion. La substitution des colonnes à garnissage par des colonnes à pulvérisation présente un intérêt économique car la surface d’échange entre les phases gazeuse et liquide est très importante réduisant ainsi la taille de la colonne d’absorption. De plus, les pertes de charge côté gaz sont évitées et les coûts de maintenance réduits. L’objectif de ces travaux de thèse est de caractériser le transfert de matière dans un spray au cours d'une absorption du CO2 par une solution aqueuse de monoethanolamine (MEA) en utilisant une nouvelle méthode.Ainsi, l’étude s’intéresse à la caractérisation locale du transfert de matière entre un spray de MEA à 30% massique et une atmosphère de CO2. Pour cela, une technique optique non-intrusive est utilisée : la réfractométrie arc-en-ciel globale (GRT). Cette technique est une mesure de l’indice de réfraction d’un ensemble de gouttes localisé dans une partie du spray. C’est donc une mesure locale dans un volume de l’ordre de quelques millimètres cubes. L’indice de réfraction d’une solution dépend de sa température et de sa concentration. Ainsi, à l’aide d’un étalonnage préalable dans un réacteur agité, les indices de réfraction des solutions aqueuses de MEA chargées sont reliés à leurs températures et à leurs concentrations de CO2 absorbé. La mesure d’indice de réfraction permet donc de suivre l’avancement du transfert de matière à travers la concentration de CO2 absorbé à une température moyenne du volume de mesure. La GRT est donc utilisée pour la mesure d’indice de réfraction au cours de l’absorption avec réaction chimique et, la quantité de CO2 captée par unité de volume est mesurée à plusieurs hauteurs de chute. Les mesures sont ensuite comparées aux prédictions d’un modèle de transfert de matière dans une goutte résolu numériquement sous COMSOL Multiphysics. Dans un deuxième temps, l’étude s’intéresse à la caractérisation du transfert de matière côté gaz en mesurant par spectrométrie infra-rouge la quantité de CO2 présente dans la phase gaz lors de l’absorption de celui-ci par une solution aqueuse de MEA à 30 % massique. Les résultats sont présentés sous forme d’efficacité de captage et un coefficient de transfert de matière côté gaz est calculé, en fonction de paramètres opératoires tels que les débits gazeux et liquide.Ces travaux de thèse, appliqués au captage du CO2, traite principalement de la mesure de transfert de matière grâce à la GRT pour la première fois utilisée à une absorption avec réaction chimique. La méthode développée permettra son utilisation pour d’autres systèmes chimique. / Pollutant capture, especially of CO2, is still a major challenge nowadays.CO2 capture based on absorption with chemical reaction by aqueous solutions of amines is the most mature technique for post-combustion gas cleaning.The substitution of packed columns by spray columns presents an economical interest since the exchange area between both gas and liquid phases is very important, reducing the size of the absorption column. In addition, gas side pressure losses are avoided and maintenance costs are reduced.The aim of this thesis is to characterize mass transfer in a spray column during a CO2 absorption by an aqueous solution of monoethanolamine (MEA) by using a new optical technique.The study focuses on the characterization of the local mass transfer between MEA spray and a CO2 atmosphere. In order to achieve this, a non-intrusive optical technique is used: Global Rainbow Technique (GRT). This technique measures the refractive index of droplets in a local portion of the spray. Therefore, the measurement is local with a volume of few cubic millimeters.The refractive index of a solution depends on its temperature and its concentration. Thus, by using a prior calibration in a stirred reactor, the refractive indices of CO2 loaded MEA solutions are correlated with their temperatures and CO2 absorbed concentration. Therefore, measuring refractive index is a measurement of mass transfer extent.GRT is then used during CO2 absorption with chemical reaction, and the amount of CO2 captured per volume unit is measured at several column heights. The experimental results are then compared with mass transfer predictions in a droplet with a model numerically solved in COMSOL Multiphysics.In another hand, gas side mass transfer is characterized by measuring the amount of CO2 in the gas phase with infrared spectrometry during CO2 absorption in an aqueous solution of 30 % MEA. The results are presented in term of capture efficiency and a gas-side mass transfer coefficient is calculated as a function of operating parameters such as gas and liquid flow rates.This work, applied to CO2 capture, deals with mass transfer measurement with GRT through a first application to absorption with chemical reaction. The developed method in this thesis will allow its use for other chemical systems.

The power sector needs to be decarbonised by 2050 to meet the global target for greenhouse gas emission reduction and prevent climate change. With fossil fuels expected to play a vital role in the future energy portfolio and high efficiency penalties related to mature CO2 capture technologies, this research aimed at evaluating the efficiency improvements and alternate operating modes of the coal-fired power plants (CFPP) retrofitted with post-combustion CO2 capture. To meet this aim, process models of the CFPPs, chilled ammonia process (CAP) and calcium looping (CaL) were developed in Aspen Plus® and benchmarked against data available in the literature. Also, the process model of chemical solvent scrubbing using monoethanolamine (MEA) was adapted from previous studies. Base-load analysis of the 580 MWel CFPP retrofits revealed that if novel CAP retrofit configurations were employed, in which a new auxiliary steam turbine was coupled with the boiler feedwater pump for extracted steam pressure control, the net efficiency penalty was 8.7–8.8% points. This was close to the 9.5% points in the MEA retrofit scenario. Conversely, CaL retrofit resulted in a net efficiency penalty of 6.7–7.9% points, depending on the fuel used in the calciner. Importantly, when the optimised supercritical CO2 cycle was used instead of the steam cycle for heat recovery, this figure was reduced to 5.8% points. Considering part-load operation of the 660 MWel CFPP and uncertainty in the process model inputs, the most probable net efficiency penalties of the CaL and MEA retrofits were 9.5% and 11.5% points, respectively. Importantly, in the CaL retrofit scenarios, the net power output was found to be around 40% higher than that of the CFPP without CO2 capture and double than that for the MEA retrofit scenario. Such performance of the CaL retrofit scenario led to higher profit than that of the 660 MWel CFPP without CO2 capture, especially if its inherent energy storage capability was utilised. Hence, this study revealed that CaL has the potential to significantly reduce the efficiency and economic penalties associated with mature CO2 capture technologies.

The new Canadian laws on CO2 emissions aim to lower the emissions of coal-fired power plants down to those of natural gas combined cycle units: 420 kg CO2/MWeh. In order to meet these requirements, calcium looping and two process variants are investigated through process simulations using Aspen Plus V8.2. The combination of calcium looping and chemical looping combustion, replacing the required air separation unit, is a way to reduce the energy penalty of the capture process. The addition of copper as an oxygen carrier in two different process configurations is compared to calcium looping and shown to reduce the efficiency penalty from 7.8% to 4.5% points but at the price of circulations rates up to about 3800 kg/s. The other improvement path studied is the implementation of calcium looping to a pressurized fluidized bed combustion unit. The pressurized carbonator acts as a reheater for the gas turbine and operating the carbonator at temperatures up to 798°C results in a reduction of the energy penalty from 5.1% to 3.1% points.

abstract: In this study, the stereolithography (SLA) 3D printing method is used to manufacture honeycomb-shaped flat sorbents that can capture CO2 from the air. The 3D-printed sorbents were synthesized using polyvinyl alcohol (PVA), propylene glycol, photopolymer resin, and an ion exchange resin (IER). The one-factor-at-a-time (OFAT) design-of-experiment approach was employed to determine the best combination ratio of materials to achieve high moisture swing and a good turnout of printed sorbents. The maximum load limit of the liquid photopolymer resin to enable printability of sorbents was found to be 44%. A series of moisture swing experiments was conducted to investigate the adsorption and desorption performance of the 3D-printed sorbents and compare them with the performance of IER samples prepared by a conventional approach. Results from these experiments conducted indicate that the printed sorbents showed less CO2 adsorptive characteristics compared to the conventional IER sample. It is proposed for future research that a liquid photopolymer resin made up of an IER be synthesized in order to improve the CO2-capturing ability of manufactured sorbents. / Dissertation/Thesis / Masters Thesis Mechanical Engineering 2020

The thesis focuses on CCS and CCU technologies, which could find application in industry and other sectors in the future. These technologies are used to reduce CO2 emissions, mainly from point sources. This thesis provides a comprehensive overview and division of CCS and CCU technologies and points out negative effects of its installation. Part of the work is also a comparison of individual steps of technology, both from an energetic and financial point of view. The aim is to show a wide range of influences on the final price and a significant discrepancy in the results of some scientific works. At the same time, in some parts, you can find a detailed description of individual parts of the technology.

Les sprays réactifs peuvent être trouvés dans de nombreuses applications industrielles. La caractérisation de l'état transitoire pour des gouttes est un défi, elle nécessite la mesure de la température et / ou des gradients de composition dans des gouttes. Dans cette thèse, la technique d'arc en ciel globale est étendue pour pouvoir quantifier l'évolution des gradients. Après l'étude numérique des caractéristiques de l'arc-en-ciel diffusé par goutte à gradient d'indice de réfraction radial, une étude expérimentale est réalisée pour le cas particulier de la capture du CO2 par des gouttes de MEA. Il a été démontré que des gradients de concentration peuvent être quantifiés lors des premiers instants de la mise en contact des gouttes avec le dioxyde de carbone. Après un temps de contact suffisamment long, l'analyse de la mesure d'arc en ciel globale basée sur des gouttes avec ou sans gradients révèle un comportement identique. / Reactive sprays can be found in numerous industries. The characterization of transient state for such droplets is a challenge, asks for the measurement of temperature and/or composition gradients inside the droplets. In this thesis, Global Rainbow Technique (GRT) is extended to be able to quantify the behavior of gradients. After the numerically studied on the characteristics of rainbow scattered by droplet with radial refractive index gradients, an experimental study is carried out for the particular case of CO2 capture by MEA droplets. According to the investigation, it is demonstrated that the gradients can be quantified during the first moments of injection. The analysis of GRT measurement based on the droplet with or without gradients indicates the identical behavior when the reacting time is long enough.