Effect of Branching on Mutual Solubility of Alkane-CO₂ Systems by Molecular Simulations

Mutual solubilities of hydrocarbon-CO₂ systems are important in a broad range of applications. Experimental data and theoretical understanding of phase behavior of large hydrocarbon molecules and CO₂ are limited. This is especially true in relation to the molecular structure of hydrocarbons when the carbon number exceeds 12. In this work, the continuous fractional component Gibbs ensemble Monte Carlo simulations are used to investigate mutual solubility of different alkane and CO₂ systems and the molecular structure. We investigate the mutual solubility of n-decane, n-hexadecane, n-eicosane, and the corresponding structural isomers in the CO₂-rich and hydrocarbon-rich phase. The focus will be solubility of the heavy normal alkanes and their structural isomers in CO₂. The simulation results are verified by comparing the experimental data when measurements are available. The simulation of phase behavior of the n-decane-CO₂ system agrees with the experiments. We also present simulation results of n-hexadecane-CO₂ and n-eicosane-CO₂ systems away from the critical region partly due to the finite size effect. We establish that solubility of the hydrocarbons in CO₂ is improved by change of the molecular structure in heavier alkanes. The enhanced solubility is limited in decane isomers, but the isomers of hexadecane and eicosane show 2- to 3-time solubility enhancement. The molecular dynamics simulations suggest that the improvement is from a higher coordination number of CO₂ for methyl (CH₃) rather than for methylene (CH₂) groups. This study sets the stage for molecular engineering and synthesis of hydrocarbons that are soluble in CO₂ not only by considering functionality but also by changing the molecular structure. The solubility enhancement is the first step in viscosification of CO₂ which broadens the use of CO₂.