Phase Behavior of Carbon Dioxide + Isobutanol and Carbon Dioxide + tert -Butanol Binary Systems

In recent years, the dramatic increase of greenhouse gases concentration in atmosphere, especially of carbon dioxide, determined many researchers to investigate new mitigation options. Thermodynamic studies play an important role in the development of new technologies for reducing the carbon levels. In this context, our group investigated the phase behavior (vapor–liquid equilibrium (VLE), vapor–liquid–liquid equilibrium (VLLE), liquid–liquid equilibrium (LLE), upper critical endpoints (UCEPs), critical curves) of binary and ternary systems containing organic substances with different functional groups to determine their ability to dissolve carbon dioxide. This study presents our results for the phase behavior of carbon dioxide + n -butanol structural isomers binary systems at high-pressures. Liquid–vapor critical curves are measured for carbon dioxide + isobutanol and carbon dioxide + tert -butanol binary systems at pressures up to 147.3 bar, as only few scattered critical points are available in the literature. New isothermal vapor–liquid equilibrium data are also reported at 363.15 and 373.15 K. New VLE data at higher temperature are necessary, as only another group reported some data for the carbon dioxide + isobutanol system, but with high errors. Phase behavior experiments were performed in a high-pressure two opposite sapphire windows cell with variable volume, using a static-analytical method with phases sampling by rapid online sample injectors (ROLSI) coupled to a gas chromatograph (GC) for phases analysis. The measurement results of this study are compared with the literature data when available. The new and all available literature data for the carbon dioxide + isobutanol and carbon dioxide + tert -butanol binary systems are successfully modeled with three cubic equations of state, namely, General Equation of State (GEOS), Soave–Redlich–Kwong (SRK), and Peng–Robinson (PR), coupled with classical van der Waals mixing rules (two-parameter conventional mixing rules, 2PCMR), using a predictive method.