A substituição da água por líquidos iônicos (LI) oferece uma alternativa promissora para o desenvolvimento de processos de separação de gases, principalmente devido à significativa demanda energética em processos convencionais que utilizam soluções aquosas de aminas. Esta proposta apresenta-se interessante por aliar as propriedades dos LI à reatividade de aminas perante o CO2. A físico-química que governa as interações entre os íons dos líquidos iônicos é bastante diversa das encontradas em solventes moleculares, sendo que ainda permanecem muitas questões fundamentais acerca destes materiais. A melhor compreensão das interações estabelecidas entre aminas e LI, e dos produtos formados após a reação com CO2, pode contribuir para o desenvolvimento de processos mais eficazes que permitam a substituição da água nos processos convencionais. O presente trabalho teve como objetivo investigar soluções das aminas primárias propilamina (PA), 2-metoxietilamina (MOEN) e monoetanolamina (MEA) em líquidos iônicos imidazólicos com diferentes ânions: 1-butil-3-metilimidazólio tetrafluoroborato (BMIBF4), hexafluorofosfato (BMIPF6), bis-(trifluorometilsulfonil)imida (BMITFSI) e dicianamida (BMIN(CN)2). Para tal, foram utilizadas as espectroscopias Raman e infravermelho (IR), cujos resultados foram suportados por cálculos baseados na teoria do funcional da densidade (DFT). Os resultados mostram que o modo de estiramento assimétrico do grupo NH2 das aminas, νas(NH2), é o mais adequado para se inferir sobre o grau de agregação das aminas em solventes orgânicos e em LI. No caso das reações das aminas com CO2 nos diferentes LI, o comportamento foi similar à reação com as aminas puras, ou seja, na PA houve cristalização, na MOEN, a formação de um líquido miscível com os LI, e na MEA, a formação de um gel com a subsequente separação de fases. Em particular, no caso da reação entre MEA e CO2 em LI, além da separação de fases, foi observada a diferente solubilidade dos produtos de reação dependendo do LI em questão. Em contraste ao processo convencional que utiliza soluções aquosas de aminas para a captura do CO2, acredita-se que a separação de fases observada em LI seja uma vantagem a ser explorada, já que permitiria um menor gasto energético na recuperação da amina absorvedora, além da recuperação do solvente não volátil / The replacement of water by ionic liquids (IL) offers a promising alternative for the development of gas separation processes, mainly due to the significant energy demand in conventional processes using aqueous solutions of amines. This proposal is exciting because it combines the properties of IL with the reactivity of amines towards CO2. The physical-chemistry that governs the interactions between the ionic liquids ions is quite different from those found in molecular solvents, and many fundamental questions still remain about these materials. A better understanding of the interactions between amines and IL, and the products formed after the reaction with CO2, may contribute to the development of more efficient processes to enable the replacement of water in conventional processes. This study aimed to investigate solutions of the primary amines propylamine (PA), 2-methoxyethylamine (MOEN) and monoethanolamine (MEA) in imidazolium ionic liquids with different anions: 1-butyl-3-methylimidazolium tetrafluoroborate (BMIBF4), hexafluorophosphate (BMIPF6), bis (trifluoromethylsulfonyl)imide (BMITFSI) and dicyanamide (BMIN(CN)2). For these purposes, the Raman and infrared (IR) spectroscopies were used, whose results were supported by calculations based on density functional theory (DFT). The results show that the asymmetric stretching mode of the amines group NH2, νas(NH2), are the most suitable for inferring the degree of aggregation of amines in organic solvents and IL. In the case of reactions of amines with CO2 in different IL, the behavior was similar to the reactions with neat amines, that is, it was observed crystallization with PA, the formation of a liquid miscible with IL in MOEN, and the formation of a gel-like product with subsequent phase separation in MEA. In particular, the case of the reaction between MEA and CO2 in IL, in addition to the phase separation, it was observed the different solubility of the reaction products depending on the IL concerned. In contrast to the conventional process using aqueous solutions of amines for the capture of CO2, it is believed that the phase separation observed in IL is an advantage to be exploited, since they allow lower energy consumption in the recovery of the amine absorber, besides the recovery of the non-volatile solvent.

Dans le contexte de l’écologie industrielle, l’objectif du projet est de récupérer du dioxyde de carbone à partir des fumées d’incinérateur de déchets industriels dangereux pour le valoriser en tant que matière première. La technologie de captage du CO2, la plus adaptée pour des fumées de postcombustion, est l’absorption du CO2 par des alcanolamines. Les fumées d’incinération de déchets dangereux présentent des particularités qui peuvent nuire au bon fonctionnement des unités de captage. Ainsi, la composition des fumées d’une usine d’incinération est caractérisée par une forte concentration en dioxygène, et enfin à la présence de NOx et SOx liée aux déchets industriels spéciaux qu’elle incinère. Le premier objectif est de déterminer l’influence des polluants (NOx, SOx) sur la dégradation de l’amine (MEA) et le second objectif est d’étudier l’impact des polluants sur la vitesse (ou flux) d’absorption du CO2 dans un solvant. / In the context of industrial symbiosis, the goal of this project is to reuse the carbon dioxide from the incinerator gas as a commercial substance. The most suitable technology of CO2 capture from postcombustion gas is the chemical absorption by alkanolamines. Some characteristics of waste incinerator gas may affect the performances of CO2 capture process. The composition of gas from industrial waste incinerator plant is characterized by a high concentration of oxygen and the presence of NOx and SOx. The first goal is to determine the influence of pollutants like NOx and SOx on the degradation of the amine and the second objective is to study the impact of pollutants on the CO2 absorption kinetics in a solvent.

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Det ständigt växande behovet av att minska CO2-utsläpp har lett till en ökad tonvikt på teknik för avskiljning av koldioxid från rökgas. MEA (monoetanolamin) anses vara riktmärket för lösningsmedel för att fånga in koldioxid på grund av dess höga absorptionshastighet. MEA är dock benäget att brytas ner, bilda giftiga biprodukter och dess regenerering har ett högt energibehov. Ett annat lösningsmedel med liknande teknisk mognad är vattenlösning med kaliumkarbonat (K2CO3) som används i den så kallade hot-potash carbonate (HPC)-processen. Emellertid är absorptionshastigheten i K2CO3-lösningen låg i jämförelse med MEA, vilket kräver tillsats av hastighetspromotorer för att öka absorptionshastigheten. Denna avhandling undersöker effekten av olika hastighetspromotorer på absorptionshastigheten av kaliumkarbonat. För detta utfördes absorptionsexperiment i laboratorieskala i en autoklavreaktor av rostfritt stål under kontrollerade förhållanden. Olika promotorer har undersökts, nämligen de organiska promotorerna glycin, piperazin och MEA, och de oorganiska promotorerna borsyra och vanadinpentoxid. Promotorkoncentrationen varierades mellan 3 vikt% till 7 vikt% samtidigt som koncentrationen av K2CO3 hölls konstant vid 25 vikt%. Driftförhållandena såsom det initiala partialtrycket av CO2 och temperaturen var respektiva 5 bar och 50 °C. De oorganiska promotorerna studerades enskilt såväl som i blandningar med K2CO3 för att studera effekten av varje promotor. De organiska promotorerna visade en signifikant förbättring av absorptionshastigheten jämfört med icke promoterad K2CO3. När det gäller de oorganiska promotorerna visade vanadinpentoxid jämförbara resultat med organiska promotorer med endast 3 vikt%. Ökad tillsatts av borsyra minskade absorptionshastigheten av lösningen promoterad av vanadin. Den experimentellt uppmätta absorptionshastigheten är anpassad till en enkel absorptionsmodell från vilken en skenbar absorptionshastighet för de främjade lösningsmedlen härleddes / The ever-growing need to reduce CO2 emissions has led to an increased emphasis on carbon capture technologies. MEA (monoethanolamine) is considered the benchmark solvent for CO2 capture due to its high rate of absorption. However, MEA is prone to degradation, forms toxic side products and its regeneration has a high energy demand. Another solvent with similar technological maturity is aqueous potassium carbonate (K2CO3) that is used in the so-called hot-potash carbonate (HPC) process. However, the rate of absorption in aqueous K2CO3 is low in comparison to MEA calling for the addition of rate promoters to enhance the absorption rate.  This thesis investigates the effect of different rate promoters on the absorption rate of potassium carbonate. For this, absorption experiments on the laboratory scale were conducted in a stainless-steel autoclave reactor under controlled conditions. Various promoters have been explored, namely the organic promoters glycine, piperazine, and MEA, and the inorganic promoters boric acid and vanadium pentoxide. The promoter concentration was varied between 3 wt% to 7 wt% while keeping the concentration of K2CO3 constant at 25 wt%. The operating conditions, such as the initial partial pressure of CO2 and the temperature were 5 bar and 50°C, respectively. The inorganic promoters were studied alone as well as in blends with K2CO3 to understand the effect of each promoter. The organic promoters demonstrated a significant enhancement of the absorption rate compared to unpromoted K2CO3. Regarding the inorganic promoters, vanadium pentoxide showed comparable results to organic promoters with only 3 wt%. When looking at the results of vanadium and boric acid, increasing concentration of boric acid resulted in a decrease in the absorption rate. The experimentally measured absorption rate are fitted to a simple absorption model from which an apparent absorption rate for the promoted solvents was derived.