Iron Release and Precipitation in Fracture Fluid-Shale Fracturing Systems

Abstract:

Hydraulic fracturing of unconventional hydrocarbon reservoirs is important to the United States energy portfolio. Hydrocarbon production from new wells generally declines rapidly over the initial months of production. One possible reason for the decrease is the mineralization and clogging of microfracture networks proximal to propped fractures. One important but relatively unexplored class of reactions is oxidation of Fe(II) derived from Fe(II)-bearing mineral dissolution (primarily pyrite and siderite) and subsequent precipitation of Fe(III)-(oxy)hydroxides. To explore this topic, we reacted fracture fluid with sand-sized and whole rock chips from four different geological localities (Marcellus Fm., Barnett Fm., Eagle Ford Fm., and Green River Fm.) containing highly varied concentrations of clays, carbonates, and TOC. Additionally, kerogen was isolated from the Green River Fm. and reacted with fracture fluid. All the shale sands showed an initial release of Fe into solution during the first 96 hours of reaction followed by a plateau or significant drop in Fe indicating that mineral precipitation occurred. Conversely, the Fe concentrations in the kerogen reactors kept increasing throughout the 3-week experiments. The whole rock samples showed a steady increase then a plateau in Fe during the 3-weeks, indicating a slower Fe release and subsequently, slower Fe precipitation. Reactors with Marcellus Fm. Sands contained dilute HCl, water only, the fracture fluid with no headspace, and fracture fluid with no HCl. Results from these experiments show that HCl is the most important additive for the promotion of Fe release into solution. Iron oxidation is not promoted solely by O₂ or organics but instead requires a combination of the two for precipitation in these systems. These results indicate that Fe redox cycling is an important and complex part of hydraulic fracturing that most likely results in production slowdown over the life of a well.