Extracting gas from unconventional shale reservoirs with low permeability is challenging. To overcome this, hydraulic fracturing (HF) is employed. Despite enhancing shale gas production, HF has drawbacks like groundwater pollution and induced earthquakes. Such issues highlight the need for ongoing exploration of novel shale gas extraction methods such as in situ heating through combustion or pyrolysis to mitigate operational and environmental concerns. In this study, thermally immature shales of contrasting organic richness from Rajmahal Basin of India were heated to different temperatures (pyrolysis at 350, 500 and 650 °C) to assess the temperature protocols necessary for hydrocarbon liberation and investigate the evolution of pore structural facets with implications for CO₂ sequestration in underground thermally treated shale horizons. Our results from low-pressure N₂ adsorption reveal reduced adsorption capacity in the shale splits treated at 350 and 500 ºC, which can be attributed to structural reworking of the organic matter within the samples leading to formation of complex pore structures that limits the access of nitrogen at low experimental temperatures. Consequently, for both the studied samples BET SSA decreased by ∼58% and 72% at 350 °C, and ∼67% and 68% at 500 °C, whereas average pore diameter increased by ∼45% and 91% at 350 °C, and ∼100% and 94% at 500 °C compared to their untreated counterparts. CO₂ adsorption results, unlike N₂, revealed a pronounced rise in micropore properties (surface area and volume) at 500 and 650 ºC (∼30%–35% and ∼41%–63%, respectively for both samples), contradicting the N₂ adsorption outcomes. Scanning electron microscope (SEM) images complemented the findings, showing pore structures evolving from microcracks to collapsed pores with increasing thermal treatment. Analysis of the SEM images of both samples revealed a notable increase in average pore width (short axis): by ∼4 and 10 times at 350 °C, ∼5 and 12 times at 500 °C, and ∼10 and 28 times at 650 °C compared to the untreated samples. Rock-Eval analysis demonstrated the liberation of almost all pyrolyzable kerogen components in the shales heated to 650 °C. Additionally, the maximum micropore capacity, identified from CO₂ gas adsorption analysis, indicated 650 °C as the ideal temperature for in situ conversion and CO₂ sequestration. Nevertheless, project viability hinges on assessing other relevant aspects of shale gas development such as geomechanical stability and supercritical CO₂ interactions in addition to thermal treatment.

Organic-rich shales are marked by the presence of complex pore structures and extremely low permeabilities, which present challenges while extracting hydrocarbon from them. With the potential negative environmental impacts of hydraulic fracturing, recent research has focused on alternative techniques such as in situ combustion/pyrolysis for enhancing the permeability of shales. In this study, low-temperature combustion was used to evaluate the evolution of pore structures in shales for contrasting thermal maturities and organic matter type from the Raniganj and Bikaner-Nagaur basins of India. The heating temperatures were decided on the basis of the combustion behavior of the samples observed from thermogravimetric analysis (TGA). Results from low-pressure N₂ and CO₂ gas adsorption indicate that mesopore and micropore structures in shales are significantly altered due to thermal treatment at higher temperatures. In general, for both of the shales, initially, when treated at lower temperatures, with respect to the raw shales, the mesopore surface area and fractal dimensions were observed to increase with lowering of pore sizes and vice versa. Similar to the mesopore trend, the increase-decrease trend of microporosity with heating was observed to be consistent for both of the shales. The oil-window mature shales showed a significant increase in micropores compared to the thermally immature shales. Microstructural investigations using high-resolution imaging also indicated a dramatic alteration of visible porosity with thermal treatment.