Carbon dioxide removal from coal power plants : a review of current capture techniques and an investigation of carbon dioxide absorption using hybrid solvents.

Abstract

The aim of this project was to identify and assess all possible solutions to reduce carbon dioxide (CO2) emissions from coal power plants in South Africa, identify the most likely solution to be implemented industrially in the short to mid-term future, and contribute towards its development through lab measurement and further research. This thesis thus contains a substantial literature review conducted on the current state of CO2 emissions in South Africa, conventional and novel coal power plant processes, modes of CO2 capture, criteria regarding the implementation of CO2 capture techniques, and the various CO2 capture techniques currently investigated with varying levels of development. The study found gas absorption using solvents to be the most likely mid-term CO2 capture technique to reach industrial implementation. However, certain challenges still need to be overcome, particularly due to numerous limitations of current solvents, to make this technique feasible for CO2 capture. In an attempt to overcome the main challenge of solvent absorption capacity, it was decided to investigate the use of ionic liquids for CO2 absorption. An in-depth review of ionic liquids was conducted, as well as a review of measurement techniques and modelling of gas absorption in alkanolamine and ionic liquid solvents. Four ionic liquids, namely methyl trioctyl ammonium bis(trifluoromethylsulfonyl)imide [MOA][Tf2N], 1-butyl-3-methyl imidazolium bis(trifluoromethylsulfonyl)imide [Bmim][Tf2N], 1-butyl-3-methyl imidazolium tetrafluoroborate [Bmim][BF4], and 1-butyl-3-methyl imidazolium methyl sulphate [Bmim][MeSO4] were tested for CO2 and O2 absorption by measuring equilibrium Pressure-Temperature-Liquid mole fraction (P-T-x) data. Measurements were conducted using an Intelligent Gravimetric Analyser (IGA-01) at 303.15, 313.15, and 323.15 K. CO2 partial pressures of 0.05 to 1.5 MPa and O2 partial pressures of 0.05 to 0.7 MPa were investigated. Furthermore, density and refractive index measurements were conducted for all solvents. The ionic liquids were benchmarked against other ionic liquids and conventional alkanolamine solvents for CO2 absorption capacity and selectivity. The study found that ionic liquids achieved higher CO2 absorption capacity at high pressure than conventional alkanolamine solvents, but very low absorption capacity at low pressure. Of the ionic liquids studied, [Bmim][BF4] and [Bmim][Tf2N] achieved high CO2 absorption and high CO2 selectivity over O2. Therefore, these two ionic liquids were selected to be combined with conventional alkanolamine solvents, namely Monoethanolamine (MEA), Diethanolamine (DEA), and Methyl Diethanolamine (MDEA), in order to form hybrid solvents. P-T-x data was obtained for CO2 absorption in alkanolamine-ionic liquid hybrid solvents containing various compositions of the above alkanolamines and ionic liquids, by gravimetric analysis, under temperature and pressure conditions as described above. CO2 absorption in the hybrid solvents was analysed, compared, and benchmarked against absorption in pure ionic liquids and conventional alkanolamine solvents. Absorption data for pure ionic liquid systems was modelled using the Redlich-Kwong equation of state (RK-EOS), while absorption in hybrid solvents was modelled using the RK-EOS for the ionic liquid components and the Posey-Tapperson-Rochelle model for the alkanolamine components of each hybrid solvent. All modelling was programmed using MatlabTM R2012B engineering programming software. Further composition analysis was intended using Fourier transform infrared (FTIR) spectroscopy. The design and development of this apparatus is described herein. The apparatus possessed limitations in achieving the desired measurements. Recommendations are described for future modifications to make the apparatus more applicable for the systems in this work. The most important conclusion was that the hybrid solvents successfully achieved higher equilibrium CO2 absorption than conventional alkanolamine solvents and pure ionic liquids, at low pressure. Absorption increased with higher temperature, lower pressure, and alkanolamine concentrations lower than 40wt%. Modelling of CO2 absorption in hybrid solvents using the above stated model proved inadequate, with deviations nearly as high as 10% of measured data. A process of CO2 capture was simulated using the engineering software Aspen Plus V8.0. CO2 absorption in the hybrid solvent containing MEA:DEA:[Bmim][BF4] at 31.8:12.1:56.1 wt% was benchmarked against CO2 absorption in a conventional alkanolamine solvent. The simulation revealed a significant improvement in CO2 absorption using the hybrid solvent at low system pressure. However CO2 selectivity and solvent recycle heat duty results were undesirable. Finally, recommendations are listed for future research endeavours, simulation and apparatus development.