Porous organic polymers containing nitrogen-rich building units are among the most promising materials for selective CO2 capture and separation applications that impact the environment and the quality of methane and hydrogen fuels. The work described herein describes post-synthesis modification of Nanoporous Organic Frameworks (NPOFs) and its impact on gas storage and selective CO2 capture. The synthesis of NPOF-4 was accomplished via a catalysed cyclotrimerization reaction of 1,3,5,7-tetrakis(4-acetylphenyl)adamantane in Ethanol/Xylenes mixture using SiCl4 as a catalyst. NPOF-4 is microporous and has high surface area (SABET = 1249 m2 g-1). Post-synthesis modification of NPOF-4 by nitration afforded (NPOF-4-NO2) and subsequent reduction resulted in an amine-functionalized framework (NPOF-4-NH2) that exhibits improved gas storage capacities and high CO2/N2 (139) and CO2/CH4 (15) selectivities compared to NPOF-4 under ambient conditions. These results demonstrate the impact of nitro- and amine- pore decoration on the function of porous organic materials in gas storage and separation application.

Porous organic polymers (POPs) with high physicochemical stability have attracted significant attention from the scientific community as promising platforms for small gas separation adsorbents. Although POPs have amorphous morphology in general, with the help of organic chemistry toolbox, ultrahigh surface area materials can be synthesized. In particular, nitrogen-rich POPs have been studied intensively due to their enhanced framework-CO2 interactions. Postsynthetic modification (PSM) of POPs has been instrumental for incorporating different functional groups into the pores of POPs which would increase the CO2 capture properties. We have shown that functionalizing the surface of POPs with nitro and amine groups increases the CO/N2 and CO2/CH4 selectivity significantly due to selective polarization of CO2 molecule. In addition, controlled postsynthetic nitration of NPOF-1, a nanoporous organic framework constructed by nickel(0)-catalyzed Yamamoto coupling of 1,3,5-tris(4-bromophenyl)benzene, has been performed and is proven to be a promising route to introduce nitro groups and to convert mesopores to micropores without compromising surface area. Reduction of the nitro groups yields aniline-like amine-functionalized NPOF-1-NH2. Adequate basicity of the amine functionalities leads to modest isosteric heats of adsorption for CO2, which allow for high regenerability. The unique combination of high surface area, microporous structure, and amine-functionalized pore walls enables NPOF-1-NH2 to have remarkable CO2 working capacity values for removal from landfill gas and flue gas. Benzimidazole-linked polymers have also been shown to have promising CO2 capture properties. Here, an amine functionalized benzimidazole-linked polymer (BILP-6-NH2) was synthesized via a combination of pre- and postsynthetic modification techniques in two steps. Experimental studies confirm enhanced CO2 uptake in BILP-6-NH2 compared to BILP-6, and DFT calculations were used to understand the interaction modes of CO2 with BILP-6-NH2. Using BILP-6-NH2, higher CO2 uptake and CO2/CH4 selectivity was achieved compared to BILP-6 showing that this material has a very promising working capacity and sorbent selection parameter for landfill gas separation under VSA settings. Additionally, the sorbent evaluation criteria of different classes of organic polymers have been compared in order to reveal structure-property relationships in those materials as solid CO2 adsorbents.

L'objectif de la thèse est d'étudier la valorisation des chars de biomasse. Dans ce contexte de transition énergétique, les biomasses sélectionnées sont les écales de sarrasin et de millet, assez pu étudiées jusqu'à maintenant, produites localement pour contribuer au développement de l'économie circulaire et qui ne compromettent pas une filière de valorisation connue. Dans ce travail, la valorisation matière est abordée à travers la réutilisation de ces résidus dans des procédés d'épuration catalytique de syngaz ou dépuration de biogaz pour lesquels les polluants sont respectivement les goudrons et le sulfure d'hydrogène. Des bilans énergétiques relatifs à la production de ces chars ont été établis et des indicateurs d'efficacité énergétiques ont été calculés. Pour ce faire, les chars ont été produits à 500 °C puis caractérisés par des analyses chimiques et physiques. Afin de leur conférer de meilleures propriétés poreuses nécessaires pour les applications d'épuration de gaz en lit fixe, des activations ont été réalisées à 850 °C avec du CO₂ ou de la vapeur d'eau. Les écales de sarrasin se révèlent être une biomasse assez classique et la particularité des écales de millet est de présenter des taux élevés en silicium. Si les chars de pyrolyse ont montré une efficacité faible dans l'épuration des gaz, l'activation leur ouvre de nouvelles potentialités, notamment pour les écales de sarrasin qui s'apparentent alors à des charbons actifs. Les chars des écales de sarrasin démontrent leur intérêt lorsqu'ils sont activés à la vapeur d'eau pour la purification du syngaz et ils conservent leur pouvoir calorifique (PCI) que permet d'envisager une valorisation énergétique par gazéification. Ces résultats montrent également qu'en fonction de la nature de la biomasse et du type d'activation, les objectifs de valorisation matière et énergie sont parfois incompatibles. / The aim of the thesis is to study the valorization of chars prepared from biomass wastes. In this context of energy transition, the selected biomasses are the buckwheat and millet husks since they are barely studied until now. In addition these wastes are produced locally, contribute to the developement of the circular economy and to not compromise a known value chain. In this word, material recovery is approcached through the reuse of these residues in syngaz and biogas cleaning processus in order to remove key pollutants such as tars and hydrogen sulfide, respectively. Energy balances form the prodution fo these chars have been established and energy efficiency indicators have been calculated. The chars were produced at 500 °C and then characterized by chemical and physical analysis. In order to provide them porous properties necessary for fixed-bed gas cleaning applications, activations were carried out at 850 °C with CO₂ or steam. Buckwheat husks turn out to be a fairly conventional biomass and the particularity of millet husks is to have high levels of silicon. If pyrolysis chars have shown a low efficiency in the purification of gases, activation opens up new potential for them, especially for materials from buckwheat husks, which are similar to activated carbons. When activated with steam these chars show interesting efficiency for the purification of syngas and they conserve their calorific value (LHV) which makes it possible to consider an energy recovery through gasification. Results from this study also show that depending on the nature of biomass and type of activation, the material valorization and energy recovery are sometimes incompatible.

Les composés traces présents dans les biogaz sont un frein à leur valorisation énergétique. Trois familles ont été identifiées comme particulièrement nocives pour les catalyseurs des reformeurs externes et pour l’anode des piles à combustible de type SOFC : les composés soufrés, siliciés et chlorés. Un traitement poussé du biogaz est donc indispensable pour une telle application. Ce travail à caractère expérimental s’intéresse au développement d’un système de traitement d’affinage destiné à l’adsorption de ces composés. Des matériaux adsorbants ont été sélectionnés pour leur efficacité dans l’élimination du sulfure d’hydrogène (H2S – composé soufré), de l’octaméthylcyclotétrasiloxane (D4 – composé silicié) et du cis-1,2-dichloroéthène (C2H2Cl2 – composé chloré), molécules cibles représentatives des trois familles préjudiciables. La zéolithe étudiée présente la meilleure efficacité d’élimination de l’H2S, tandis que le gel de silice est plus adapté à l’adsorption du D4. Une étude paramétrique a mis en évidence l’influence de la hauteur de lit d’adsorbant, de la concentration en polluant, du débit de gaz, de la présence de composés traces en mélange et de l’humidité sur les performances épuratoires. Des essais sur un biogaz brut d’installation de stockage de déchets non dangereux ont montré qu’il est possible de maintenir une concentration en H2S sous le seuil de tolérance de 1 ppmvH2S du reformeur. En s’appuyant sur des caractérisations physico-chimiques des adsorbants, des hypothèses concernant les mécanismes de rétention ont été proposées pour les couples zéolithe + H2S et gel de silice + D4. L’H2S est adsorbé puis oxydé en soufre élémentaire à la surface de la zéolithe. Lors de l’adsorption sur gel de silice, le D4 semble polymériser en surface. Ces deux phénomènes empêchent la régénération des adsorbants. Une première approche de modélisation des phénomènes d’adsorption pour le couple gel de silice + D4 a permis de déterminer le coefficient global de transfert de masse. Les courbes de percée obtenues expérimentalement pour différentes masses d’adsorbant ont été simulées avec succès. Des « règles de dimensionnement » ont été proposées pour un dimensionnement industriel d’un traitement d’affinage pour une valorisation en SOFC. L’analyse technico-économique a montré que la filière SOFC envisagée est viable techniquement, mais pas économiquement, la technologie SOFC étant encore trop coûteuse par rapport aux techniques de valorisation conventionnelles. Toutefois, la solution semble prometteuse d’un point de vue environnemental. / Biogas energy use is hampered by the presence of trace compounds. Three contaminant families are particularly detrimental for external reforming catalysts and solid oxide fuel cell (SOFC) anodes: sulfur-containing compounds, volatile organic silicon compounds (VOSiC) and chlorinated compounds. Therefore, a thorough biogas treatment is necessary for such an application. This experimental work deals with the development of a polishing treatment for the adsorption of these contaminants. Adsorbents were selected for their efficiency to remove hydrogen sulfide (H2S – sulfur-containing compound), octamethylcyclotetrasiloxane (D4 – VOSiC) and cis-1,2-dichloroéthene (C2H2Cl2 – chlorinated compound), molecules representative of the three harmful families. The studied zeolite showed the best efficiency for H2S removal whereas silica gel performed best for D4 adsorption. A parametric study highlighted the influence of adsorbent bed height, contaminant concentration, gas flow rate, the presence of contaminants in mixture and humidity on purification performance. Adsorption tests with a raw landfill biogas showed that it is possible to guarantee an H2S concentration below the 1 ppmvH2S tolerance limit of the reformer. Using adsorbent physicochemical characterizations, hypothesis about retention mechanisms were proposed for the couples zeolite + H2S and silica gel + D4. H2S is adsorbed and then oxidized into elemental sulfur at the surface of the zeolite. During the adsorption on silica gel, D4 seems to polymerize on the surface. These two phenomena prevent the regeneration of the adsorbents. A first modeling approach of the adsorption phenomena involved for the couple silica gel + D4 allowed the determination of the global mass transfer coefficient. Experimental breakthrough curves obtained for different masses of adsorbent were successfully simulated. Some “dimensioning rules” were proposed for the industrial design of a polishing treatment able to produce a biogas with the quality required to feed an SOFC. The techno-economic analysis showed that the SOFC solution is technically feasible but not economically viable because SOFC technology is still too costly compared to conventional conversion devices. However, the solution seems promising from an environmental point of view.

Treatment of fuel cell feed H2 for the removal of CO is important owing to the poisoning of the catalysts, thereby affecting the performance of the fuel cell. Strong and preferential adsorption of CO over the catalyst takes place resulting in a reduction of the power output of the cell. Therefore, it is important to treat the fuel cell feed H2 to reduce its CO content below the tolerable limit. Development of efficient catalysts for the treatment of synthesis gas for the removal of CO and and H2 enrichment of the gas to make it suitable for fuel cells is one of the two goals of this thesis. One of the various possible strategies for the removal of CO from the synthesis gas can be the use of the water-gas shift reaction. We have developed noble metal substituted ionic catalysts for catalyzing the water-gas shift reaction and have studied in detail the kinetics of the reactions by proposing the relevant reaction mechanisms. Solution combustion, a novel technique for synthesizing nanocrystalline materials, was used for the synthesis of all the catalysts. All the compounds synthesized were solid solutions of the noble metal ion and transition or rare earth metal oxide support. Three different supports were used, viz., CeO2, ZrO2 and TiO2. Substitution of Zr and Ti in CeO2 up to 15 at% was also carried out to obtain the compounds with enhanced oxygen storage capacity. All the compounds were characterized by X-ray diffraction, X-ray photoelectron spectroscopy and transmission electron microscopy. In some cases, where it was required, the use of FT-Raman spectroscopy was made for structural analysis. The compounds were nanocrystalline with metals substituted in ionic form in the support. The water-gas shift reaction was carried out over the synthesized catalysts with a reactant gas mixture that simulated the actual refinery gas composition. The variation of CO concentration with temperature was traced. The changes in the oxidation state of the metal showed the involvement of the various redox pairs over the reducible oxide like substituted CeO2 and TiO2. The mechanism of the reaction over ZrO2-based compounds was found to take place utilizing the surface hydroxyl groups. Rate expressions for the reactions over all the catalysts following different mechanisms were derived from the proposed elementary processes. Nonlinear regression was used for the estimation of various parameters describing the rate of reaction. Having established the high activity of Pt-ion substituted TiO 2 for the reactions, steam reforming of wood gas obtained from the gasification of Casuarina wood chips was carried out. The enrichment of the gas stream, which initially consisted of nearly 10% H 2 was carried out by steam reforming and H2-rich stream was obtained with H2 as high as 40% by volume in the treated gas. The second motive behind this thesis was to test the activity of the noble-metal substituted ionic catalysts for the treatment of the exhaust gas coming out of a fuel cell. In the fuel cell utilizing H2, the exhaust gases contain certain amount of unreacted H2, which can not be recovered or utilized economically. However, the gases are combustible and H 2 has to be removed in order to make the gas clean. We have shown high activity of the combustion-synthesized ionic compounds for catalytic combustion of H2. All the compounds showed high activity for H2 combustion and complete removal of H2 was possible. The rates were found to increase with an decrease in H2:O2 ratio and complete conversion of H2 was possible within 100 oC with air. A mathematical model was developed for the kinetics of catalytic H2 combustion based on the elementary processes that were proposed using the spectroscopic evidences. CO tolerant capacity of the catalysts was also tested. It was found that the temperature requirement for most of the catalysts increased with the introduction of CO. However, it was still possible to obtain complete conversions within 200 oC. To summarize, fuel cell processing systems utilizing H 2 remained central to the study. Treatment of the gases, both before and after reaction from the fuel cell was carried out over noble metal-substituted ionic catalyst, synthesized by solution combustion technique. Mechanisms of the reactions were proposed on the basis of spectroscopic evidences and the kinetic rate parameters were estimated using non-linear regression.

La forte augmentation de la population mondiale entraîne une demande croissante en eau potable. La production d'eau potable est accompagnée par la génération de résidus du traitement de l'eau dont la boue d'aluminium qui est donc largement disponible mondialement. Ce travail se concentre sur l'identification des différentes voies de valorisation des boues d'aluminium afin de les réutiliser dans le domaine de l’environnement. Deux sources de boues d'aluminium, collectées en France et en Irlande, ont été étudiées dans divers domaines d’application en fonction de leurs caractéristiques. Tout d'abord, les boues d'aluminium ont été utilisées en remplacement d’une partie de l'argile dans la fabrication des briques, en incorporant différents pourcentages de boues d'aluminium et à différentes températures. Les briques résultantes ont été caractérisées et les résultats ont montré que les briques composées de boues d'aluminium et d'argile sont conformes aux « normes européennes et irlandaises » et démontrent ainsi le potentiel pour une application industrielle des boues d'aluminium dans la fabrication de briques en terre cuite irlandaises. Dans un second temps, les boues d’aluminium ont été utilisées comme adsorbant des polluants présents dans l’agriculture. Le glyphosate est un ingrédient actif dans les pesticides utilisés massivement dans l'agriculture irlandaise et représente une problématique environnementale. La boue d’aluminium et la tourbe irlandaise ont été comparées pour l’élimination du glyphosate lors de tests en pot à l’échelle laboratoire. Les résultats ont montré que la boue d’aluminium permet d’éliminer le glyphosate à plus de 99% et réduire les niveaux de DCO. Cet aspect scientifique a permis d’être dans la sélection des adsorbants possibles pour le traitement des eaux usées agricoles en Irlande. Le co-conditionnement et la déshydratation des boues de station d’épuration avec des boues d’aluminium liquides ont également été étudiés. Pour cela, le Jar test a été effectué sur des boues issues d’une station de traitement des eaux française. Les résultats ont montré que le rapport optimal de mélange des boues est de 1:1 (boues d’épuration : boues d’aluminium). Ainsi, la quantité de polymère utilisée peut être diminuée de 14 fois par rapport aux technologies actuelles. Cette approche a permis de montrer la possible valorisation des boues d’aluminium comme un moyen durable et technique permettant ainsi l’élimination des boues localement pour une même station de traitement des eaux. Une autre voie de valorisation des boues d’aluminium comme adsorbant pour la purification des gaz a été étudiée lors d’expériences d’adsorption de H2S dans un réacteur à lit fixe dans différentes conditions expérimentales. Les données expérimentales d’adsorption du H2S ont été modélisées à l'aide de modèles empiriques basés sur la cinétique des processus d'adsorption. Les résultats ont montré que les boues d'aluminium sont un adsorbant efficace pour l'élimination du H2S (capacité de 374,2 mg H2S / g solide) et que des mécanismes mis en jeu sont l'adsorption dissociative et l'oxydation. Les coefficients de transfert de masse globaux ont également été calculés et pouvant ainsi être utilisés pour la prédiction. Enfin, les gâteaux de boues d'aluminium ont été réutilisés pour la purification simultanée d’H2S et le traitement des eaux usées. Les résultats ont montré la capacité de cet adsorbant pour éliminer tout le H2S présent avec une grande efficacité d’élimination de la DCO, TN et TP. Ainsi, il a été démontré la valorisation des boues d’aluminium en tant qu’adsorbant pour une purification du H2S simultanée avec le traitement des eaux usées. / The production of drinking water always accompanied by the generation of water treatment residues (WTRs). Alum sludge is one of the WTRs, it is an easily, locally and largely available by-product worldwide. This work focuses on the identification of different ways to valorize the alum sludge for environmentally friendly reuse. Two alum sludges collected from France and Ireland have been reused in various fields as a function of their characteristics. Firstly, alum sludge was used as a partial replacement for clay in brick making, by incorporating different percentages of alum sludge and calcined at different temperatures (range from 800 to 1200 °C). The resultant bricks were tested for compression, Loss on Ignition, water absorption, appearance, etc. Results show that alum sludge-clay bricks have met the “European and Irish Standards” and demonstrated the huge industrial application potential for alum sludge in Irish clay brick manufacturing. Glyphosate is an active ingredient in pesticide which is massive employed in agriculture. Alum sludge and Irish peat were compared for glyphosate removal in pot tests, results show that alum sludge present significant glyphosate removal capacity (>99 %) and could reduce the level of Chemical Oxygen Demand (COD). It provided a scientific clue for sorbents selection when considering the agricultural wastewater treatment in Ireland and to maximize their value in practice. The co-conditioning and dewatering of sewerage sludge with liquid alum sludge was also investigated in Jar-test based on the case analysis of a water industry in France. Results show that the optimal sludge mix ratio is 1:1, the use of the alum sludge has been shown to beneficially enhance the dewaterability of the resultant mixed sludge, and highlighting a huge polymer saving (14 times less than the current technologies) and provided a sustainable and technical sludge disposal route for the local water industry. The use of alum sludge as a sorbent for gas purification was studied by H2S adsorption experiments in a fixed-bed reactor with various operating parameters. The experimental breakthrough data were modeled with empirical models based on adsorption kinetics. Results show that alum sludge is an efficient sorbent for H2S removal (capacity of 374.2 mg/g) and the mechanisms including dissociative adsorption and oxidation were proposed. Moreover, the overall mass transfer coefficients were calculated which could be used for the process scaling up. Finally, alum sludge cakes were reused in the novel aerated alum sludge constructed wetland (CW), which were designed for simultaneous H2S purification and wastewater treatment. Results show that H2S was completely removed in the six months’ trials, while the high removal efficiencies of COD, total nitrogen (TN), total phosphates (TP) were achieved. Thus, a novel eco-friendly CW for simultaneous H2S purification and wastewater treatment was developed. In the different approaches and process considered, in particular it was put in investigating and describing the mechanisms involved. Overall, this work demonstrated alum sludge could be a promising by- product for various novel beneficial reuse rather than landfilling and provided a “Circular Economy” approach for WTRs management.