Direct Thickening of Supercritical Carbon Dioxide Using CO2-Soluble Polymer

Abstract

Two major applications of injecting dense carbon dioxide (CO2) into the petroleum reservoirs are enhanced oil recovery and sequester CO2 underground. For enhanced oil recovery applications, CO2 has low miscibility pressure causing the swelling of crude oil and reducing its viscosity therefore improving the macroscopic sweep process. However, the low viscosity of injected CO2 compared with the reservoir fluids causes the fingering of CO2, which may lead to bypassing huge amount of oil, early breakthrough of CO2, and increasing the gas to oil ratio (GOR). The use of direct thickeners, such as polymers, is one of the techniques used to increase the CO2 viscosity. Nevertheless, the solubility of polymers in CO2 and the high cost of soluble polymers are the main challenges facing this technique. In this study, a novel, soluble, and cost-effective thickener is proposed to directly increase the CO2 viscosity. In this study, a PVT high pressure and high temperature (HPHT) apparatus was used to evaluate the compatibility and the solubility of the thickener in dense CO2. Also, a custom designed apparatus was used to measure the viscosity of dense CO2 in the presence of the thickener at different conditions. The assessment was conducted at different experimental pressures, temperatures, and thickener concentrations. The effect of pressure on the solubility of the thickener in CO2 and on the measured viscosity of CO2 was evaluated at 1500, 2000, 2500, and 3000 psi. Also, the influence of temperature was evaluated at 25 and 50°C. Moreover, the concentrations used to study the effect of thickener concentration on the measured viscosity of CO2 ranged between 0.10-2 %. The results from laboratory experiments clearly demonstrated that the addition of the thickener at certain conditions can significantly impact the dense CO2 viscosity. The results revealed that there must be a minimum pressure at which the thickener dissolves in the dense CO2. The solubility of the thickener can occur when the CO2 is either in the liquid or supercritical phase. The results also pointed out that the CO2 viscosity increased as the pressure increased. The increase of CO2 pressure can significantly impact the solubility of the thickener in the dense CO2 and consequently the CO2 viscosity. The increase of the thickener concentration also had a significant impact on the measured CO2 viscosity. The results showed that the CO2 viscosity increased with the thickener concentration. The CO2 viscosity increased 100 to 1200 -fold as a result of adding the thickener depending on the experimental conditions

Thickening CO2 with Direct Thickeners, CO2-in-Oil Emulsions, or Nanoparticle Dispersions: Literature Review and Experimental Validation

“…Unfortunately, a small piece of undissolved polymer became lodged between our aluminum cylinder and the Pyrex wall of our windowed viscometer and we were unable to obtain falling cylinder apparent viscosity values during several attempts. However, such C/O waterless emulsions can exhibit high apparent viscosity, and a prior report of high viscosity of CO 2 that was “thickened” by PSM may have been attributable to the high apparent viscosity of indirectly thickened CO 2 (a C/O emulsion) such as those we previously reported (Alzobaidi et al). Alternately, the sample of PSM that we received from the manufacturer may have differed significantly from that used by Al Yousef and coworkers …”

“…However, such C/O waterless emulsions can exhibit high apparent viscosity, and a prior report of high viscosity of CO 2 that was “thickened” by PSM may have been attributable to the high apparent viscosity of indirectly thickened CO 2 (a C/O emulsion) such as those we previously reported (Alzobaidi et al). Alternately, the sample of PSM that we received from the manufacturer may have differed significantly from that used by Al Yousef and coworkers …”

“…(It is likely that with improved mixing, the mixture would have been more homogeneous throughout the entire sample volume.) The mixture was not a transparent single-phase CO 2 -rich solution; therefore, the sample of PSM that we received was not a direct thickener as described by Al Yousef . However, it could be considered as an indirect thickener that slowly established a waterless, C/O emulsion with a very high volume fraction (quality) of liquid CO 2 .…”

“…A recent study employed a polymer-based CO 2 direct thickener composed of “a mixture of different compounds including copolymers of allenethers, acrylate, acrylic long carbon chain esters/benzenes, propylene carbonate/allyl ethyl carbonate, dimethyl carbonate, and white oil/silicon or oil/petroleum ether.” (We believe that “allenether” may be a typographical error, perhaps referring to “allyl ether”.) The authors called this mixture a “direct thickener” and stated that it was soluble in CO 2 , formed a stable and homogeneous solution during a 24 h observation, and resulted in 100–1,200-fold increases in viscosity at concentrations up to 2 wt % as determined with a Cambridge viscometer.…”

“…Quite recently a proprietary direct-thickening product for CO 2 was described. This polymer–solvent mixture (PSM) consisted of “a mixture of different compounds including copolymers of allenethers, acrylate, acrylic long carbon chain esters/benzenes, propylene carbonate/allyl ethyl carbonate, dimethyl carbonate, and white oil/silicon or oil/petroleum ether” .…”