title: CO₂ capture using ionic liquids: thermodynamic modeling and molecular dynamics simulation.
Creators: name: Aghaie Moghanjoghi, Mahsa
Publisher: name: Memorial University of Newofundland
Year: 2020

description: Global climate change is happening now, and the average temperature of Earth is rising. Several evidences show that one of the main reasons for global warming is the increased concentration of greenhouse gases (GHGs) in the atmosphere, particularly carbon dioxide (CO₂). CO₂ is mostly producing from burning fossil fuels. One of the effective strategies to reduce CO₂ emissions is implementing carbon capture in fossil fuel power plants. Current post-combustion carbon capture techniques typically employ amine-based solvents, such as monoethanolamine (MEA), for the absorption of CO₂. Although alkanol amines have an acceptable absorption capacity, their high vapor pressure, solvent loss during desorption, and high corrosion rate make amines absorption plants energy-intensive. In recent years, Ionic Liquids (ILs) have been emerged as promising alternative solvents for physisorption and chemisorption of acid gases due to their unique physiochemical properties, including negligible vapor pressure, high thermal stability, tunability, and being environmentally safe. ILs require to be screened based on technical, economical, and environmental aspects. The main challenges of using ILs are increasing CO₂ capture capacity of ILs, and detailed understanding of the diffusivity of CO₂ in ILs, the effect of additives in solubility, selectivity features of ILs, phase behavior of gas-IL systems, and absorption mechanism. These challenges can be addressed using either experiment, thermodynamic modeling, and/or molecular simulations. In this study, the potential of the screened imidazolium-based ILs is investigated using thermodynamic modeling. The extended Peng–Robinson (PR) and Perturbed-Chain Statistical Associating Fluid Theory (PC-SAFT) EOSs are implemented to evaluate the solubility and selectivity of CO₂ in pure ILs and their mixture with water and toluene. The effects of water and toluene on solubility and viscosity of ILs are investigated. Low concentrations of water (< 1 wt%) do not affect solubility; however, with increasing water concentration, the solubility of CO2 is decreased. On the other hand, with increasing water content, the IL viscosity significantly decreases, which is in the favor of using viscous ILs for CO₂ separation. In this thesis, Molecular Dynamics (MD) simulation is performed to determine the properties of ILs ([Bmim][BF₄] and [Bmim][Ac]), their structures, and molecular dynamics. A great agreement is noticed between the density and viscosity of the studied ILs from MD simulations and experimental data, indicating the accuracy of our simulation runs. This study also includes the effect of temperature and anion type on the structuring of ions and their self-diffusivities. Bulk systems of ILs and CO₂ are studied to evaluate the influence of temperature and types of ions on the diffusivity of CO₂ in the solvent as well as structural characteristics. A comprehensive analysis of the characteristics of the interface of IL/CO₂ is performed to explore species distribution, gas behavior at the interface, and molecule orientation. At the interface, CO₂ creates a dense layer which interrupts the association of cations and anions, leading to a decrease in the surface tension. In addition, a comprehensive study on hydrophilic IL, 1-Butyl-3-methylimidazolium acetate or [Bmim][Ac], is conducted to evaluate the thermophysical properties, excess energy, structure, and dynamic characteristics of IL/Water and IL/Water/CO2 systems, using MD simulation approach. The effect of water on radial distribution functions, coordination numbers, water clusters, hydrogen bonding, and diffusivity coefficients of the ions is assessed. The presence of water in IL mixture, even at high concentrations of water (>0.8 mole fraction), increases the diffusivity of cation, anion, water, and CO2 molecules in the mixture due to hydrophilicity of [Bmim][Ac] IL. MD simulations generate reliable and accurate results while dealing with systems including water, CO₂, and IL for carbon capture. In this thesis, novel and robust computational approaches are also introduced to estimate the solubility of CO₂ in a large number of ILs within a wide range of temperatures and pressures. Four connectionist tools- Least Square Support Vector Machine (LSSVM), Decision Tree (DT), Random Forest (RF), and Multilinear Regression (MLR)- are employed to obtain CO₂ solubility in a variety of ILs based on thermodynamic properties and Quantitative Structure-Activity Relationship (QSPR) model. Among different types of descriptors, the most important input variables (e.g., Chi_G/D 3D and Homo/Lumo fraction (anion); SpMax_RG and Disps (cation)) are selected using Genetic Algorithm (GA)-MLR method. A great agreement between the predicted values and experimental measurements is attained while using RF and DT techniques developed based on descriptors and thermodynamics properties. The structural descriptors-based models are more accurate and robust than those built on critical properties.