Proppant Diagenesis in Carbonate-Rich Eagle Ford Shale Fractures

Proppant diagenesis occurs when minerals form on the proppant surface and/or around the embedment crater at high-temperature and/or high-stress conditions (Weaver et al. 2005). It has been used recently to explain low fracture conductivity in the field as well as the long-term downward trend of laboratory-measured American Petroleum Institute conductivity data (Liang et al. 2015). However, researchers disagree about the source of such overgrowth minerals and the involvement of proppant in the process. In addition, the diagenesis process has not been investigated in the case of carbonate-rich shale formations. Therefore, the objectives of this paper are to experimentally investigate the proppant diagenesis process during hydraulic fracturing of the Eagle Ford Shale Formation and to determine the role of the proppant in the process. Diagenesis was studied after aging a mixture of proppant and formation samples in deionized water for 3 weeks at 325°F and 300 psia. Outcrop cores of the Eagle Ford Shale Formation were crushed and sieved to 50/100 US-mesh size. The ceramic, sand, and resin-coated-sand (RCS) proppants of 20/40 US-mesh size were tested. The proppant surface was studied for mineral overgrowth and/or dissolution before and after aging using scanning electron microscope (SEM) with energy-dispersive X-ray spectroscopy (EDS). The concentration of the cations leached into the solution was measured by analyzing the supernatant samples using inductively coupled plasma (ICP)/optical-emission spectroscopy, while the sulfate-ion concentration was measured using a spectrophotometer. The proppants and the Eagle Ford Shale Formation samples were analyzed after aging separately at the same conditions to explain the sources of the leached ions and the observed overgrowth and/or precipitated minerals. The Eagle Ford Shale was found to be the source of calcium sulfate and calcium zeolite precipitates because of dissolution/precipitation reactions with water. Only the ceramic proppant was found to induce an additional mineral overgrowth of iron calcium zeolite on its surface. Conversely, the sand and RCS proppants did not encounter any precipitates/overgrowth minerals. These proppants only changed the elemental composition of the precipitated zeolite from the formation/fluid interaction, showing increased silicon and decreased calcium and aluminum concentrations. The proppant dissolution was observed with all types of proppants, as indicated by the presence of silicon ions in the solution after aging. A thermodynamic modeling study was conducted and confirmed the possibility of formation of the observed precipitate and overgrowth minerals at the equilibrium state of the rock and proppant mixture in water. Finally, the breaking and peeling of the phenol formaldehyde resin from the RCS proppant particles at static conditions was observed for the first time (to the best of the authors’ knowledge) using the SEM technique. The study contributes to the understanding of the scale formation and the mechanisms that damage fracture conductivity in the Eagle Ford Shale. Results impact the choice of fluid and proppant for fracturing optimization and long-term production sustainability in the Eagle Ford Shale reservoirs.