Multi-scale pore structure transformation of shale under mixed acid acidification method

Abstract

Most of the acid fluids used in the existing acidfrac process have the shortcomings of plugging pores, polluting formation and poor effect. The method of adding nitric acid in a specific proportion to conventional acid can avoid the above problems to a certain extent. A mixture of HCl: HF: HNO3 (3:1:1) was used to acidize the shale of the Longmaxi Formation in Sichuan and the Piyuancun Formation in Jiangxi for 24 h. The mineral fractions and pore structures of the samples were then analyzed using scanning electron microscopy-energy dispersive spectrometry, X-ray diffraction, low-pressure nitrogen adsorption, and nuclear magnetic resonance. The results showed that by reducing the mineral constituents of shale, the 2–15-nm sized pores decreased, 1–10-μm sized pores increased, and fractal dimensions decreased. The mixed acid solution caused cross-scale porosity expansion in the shale and increased gas circulation within the matrix. The process of acid mixing in the shale pore structure was divided into four stages: surface dissolution, macroporous dissolution, meso–microporous dissolution, and feedback dissolution.