Alterations of Carbonate Mineral Matrix and Kerogen Micro-Structure in Domanik Organic-Rich Shale during Anhydrous Pyrolysis

Abstract

The study of organic-rich carbonate-containing shales after heating is an important task for the effective application of in-situ thermal kerogen conversion technologies implemented for these types of rocks. This research was conducted to study changes in the rocks of the Domanik Formation after high-temperature treatment, taking into account the nature of structural changes at the micro level and chemical transformations in minerals. The sample of organic-rich carbonate-containing shales of the Domanik Formation was treated in stages in a pyrolizer in an inert atmosphere in the temperature range of 350–800 °C for 30 minutes at each temperature. By means of X-ray powder diffractometry (XRPD), HAWK pyrolysis, light and scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), and computed micro-tomography, the characteristics of the rock before and after each heating stage were studied. The results showed significant alteration of the mineral matrix in the temperature range 600–800 °C, including the decomposition of minerals with the formation of new components, and structural alterations such as fracturing micropore formation. The organic matter (OM) was compacted at T = 350–400 °C and fractured. The evolution of void space includes fracture formation at the edges between rock components, both in organic matter and in minerals, as well as nanopore formation inside the carbonate mineral matrix. The results obtained show what processes at the microlevel can occur in carbonate-containing organic-rich shales under high-temperature treatment, and how these processes affect changes in the microstructure and pore space in the sample. These results are essential for modeling and the effective application of thermal EOR in organic-rich shales.