Energy & Fuels, Vol.34, No.11, 14109-14123, 2020
Study of Liquid-Liquid and Liquid-Liquid-Vapor Equilibria for Crude Oil Mixtures with Carbon Dioxide and Methane Using Short-Wave Infrared Imaging: Experimental and Thermodynamic Modeling
In this work, phase behavior was analyzed for recombined mixtures of a Brazilian pre-salt crude oil with carbon dioxide and methane. This oil was sampled at stock tank conditions during a well-test, and mixtures with gas were prepared with a gas molar composition ranging from 20.0 to 86.0 mol %. Their phase behavior was investigated from 293.15 to 378.15 K and up to 100.0 MPa. Direct phase transition detections were achieved by using a full visibility PVT cell, coupled with a short-wave infrared camera. At this wavelength, crude oil has a lower absorbance, and it has been noted that macroscopic phase transitions can be easily detected by visual inspection. For the pseudo-binary system crude oil + carbon dioxide systems, liquid-liquid phase transitions were observed when the gas content is higher than 70.0 mol %. In addition, at the higher carbon dioxide composition, an asphaltic phase was formed at high pressures together with liquid-liquid phases. Similarly, crude oil and methane systems presented a liquid-liquid immiscibility region at methane composition above 60.0 mol % in all temperature domain studied. The Peng-Robinson equation of state was used for modeling purposes, and liquid-liquid and liquid-liquid-vapor transitions were qualitatively described. Additionally, it was observed that liquid-liquid equilibria behavior was highly dependent on the crude oil heavy fraction immiscibility because of the increasing system asymmetry by increasing mixture gas content.