Improving Long-Term Hydraulic Fracture Conductivity in Carbonate Formations by Substitution of Harder Minerals

Abstract

Hydraulic fracturing is applied in tight formations to create conductive paths within the reservoir. However, the conductivity of the created fractures declines with time due to the closure stresses. The decline is sharp in soft formations because of proppant embedment and fracture surface asperities failure. The improvement in fracture surface hardness can mitigate the abovementioned challenges and sustain the fracture conductivity. This research targeted enhancing carbonate rock's hardness by forming minerals harder than calcite. Carbonate rocks, namely dolomite, limestone, and chalk, were treated at ambient temperature conditions by immersion into the aqueous solutions of NaF and ZnSO4 with a concentration of 0.1M. During treatment, the solution was sampled to monitor the changes in ion concentration and estimate the reaction kinetics by ICP - OES and IC devices. The hardness of rock samples was measured by impulse hammering technique before and after the treatment. The changes in rock's mineralogy and elemental content were studied by XRD and SEM imaging. The permeability of rocks was estimated by the steady-state gas injection method. The formation of smithsonite (ZnCO3, Mohs scale hardness - 4.5) and fluorite (CaF2, Mohs scale hardness - 4) was achieved in the reaction of calcite (CaCO3, Mohs scale hardness – 3) with ZnSO4 and NaF, respectively. Chalk and limestone reacted efficiently with both solutions; however, the dolomite reaction with solutions was feeble. XRD detected the newly formed smithsonite minerals, and it was observed in SEM images that minerals formed an interconnected net in chalk and limestone specimens. In dolomite samples, the minerals formed isolated gatherings that were sparsely located on the grains. The treatments caused the improvement of the rock specimen's hardness. 0.1M solution of NaF was not effective in strengthening the rock samples (only chalk sample experienced 6.7% improvement in hardness) because of low concentration of the solutions used; however, treatment resulted in negligible changes in permeability of the samples. In contrast, Young's modulus of limestone and chalk treated by ZnSO4 increased by 17% and 21%. Permeability of rocks treated by ZnSO4 reduced drastically, most likely due to the formation of gypsum as a byproduct of the reaction. This research presents a method for carbonate rock hardening via the transformation of parent calcite into harder minerals. It explains its possible application in the petroleum industry to sustain the conductivity of propped/acid fractures. The proposed technique will help to mitigate fracture conductivity decline due to proppant embedment and asperities failure issues that are especially severe in soft formations.

Carbonate Rock Chemical Consolidation Methods: Advancement and Applications

“…Further attempts in carbonate rock strengthening through mineral alteration included their treatment by sodium fluoride [NaF] which results in formation of fluorite [CaF 2 ] in the following reaction with calcite: , …”