Microstructure Evolution of Organic Matter and Clay Minerals in Shales with Increasing Thermal Maturity

As the two important components of shale, organic matter(OM) and clay minerals are usually thought to strongly influence the hydrocarbon generation, enrichment and exploitation. The evolution process of OM and clay minerals as well as their interrelationship over a wide range of thermal maturities are not completely clear. Taking Yanchang(T3y), Longmaxi(S1l) and Niutitang(?1n) shales as examples, we have studied the microstructure characteristics of OM and clay minerals in shales with different thermal maturities. The effects of clay minerals and OM on pores were reinforced through sedimentation experiments. Using a combination of field emission scanning electron microscopy(FESEM) and low-pressure N2 adsorption, we investigated the microstructure differences among the three shales. The results showed that both OM and clay minerals have strong effects on pores, and small mesopore(2–20 nm) is the dominant pore component for all three samples. However, the differences between the three samples are embodied in the distribution of pore size and the location. For the T3y shale, clay minerals are loosely arranged and develop large amounts of pores, and fine OM grains often fill in intergranular minerals or fractures. Widespread OM pores distribute irregularly in S1l shale, and most of the pores are elliptical and nondirectional. The ?1n shale is characterized by the preferred orientational OM-clay aggregates, and lots of pores in the composites are in the mesopore range, suggesting that over maturity lead to the collapse and compaction of pores under huge pressure of strata. The results of the current research imply that with increasing thermal maturity, OM pores are absent at low maturity(T3y), are maximized at high maturity(S1l) and are destroyed or compacted at over-mature stage(?1n). Meanwhile, clay minerals have gone through mineral transformation and orientational evolution. The interaction of the two processes makes a significant difference to the microstructure evolution of OM and clay minerals in shale, and the findings provide scientific foundation in better understanding diagenetic evolution and hydrocarbon generation of shale.

The effects of clay minerals and organic matter on nanoscale pores in Lower Paleozoic shale gas reservoirs, Guizhou, China

In organic-rich gas shales, clay minerals and organic matter(OM) have significant influences on the origin, preservation, and production of shale gas. Because of the substantial role of nanoscale pores in the generation,storage, and seepage of shale gas, we examined the effects of clay minerals and OM on nanoscale pore distribution characteristics in Lower Paleozoic shale gas reservoirs.Using the Niutitang and Longmaxi shales as examples, we determined the effects of clay minerals and OM on pores through sedimentation experiments. Field emission–scanning electron microscopy combined with low-pressure N2 adsorption of the samples before and after sedimentation showed significant differences in pore location and pore size distribution between the Niutitang and Longmaxi shales. Nanoscale pores mostly existed in OM in the Longmaxi shale and in clay minerals or OM–clay composites in the Niutitang shale. The distribution differences were attributed largely to variability in thermal evolution and tectonic development and might account for the difference in gas-bearing capacity between the Niutitang and Longmaxi reservoirs. In the nanoscale range, mesopores accounted for 61–76% of total nanoscale pore volume.Considerably developed nanoscale pores in OM were distributed in a broad size range in the Longmaxi shale, which led to good pore connectivity and gas production.Numerous narrow pores(i.e., pores \ 20 nm) in OM–clay composites were found in the Niutitang shale, and might account for this shale's poor pore connectivity and low gas production efficiency. Enhancing the connectivity of the mesopores(especially pores \ 20 nm and those developed in OM–clay composites) might be the key to improving development of the Niutitang shale. The findings provide new insight into the formation and evolutionary mechanism of nanoscale pores developed in OM and clay minerals.

The new multistage water adsorption model of Longmaxi Formation shale considering the spatial configuration relationship between organic matter and clay minerals

The water adsorption by shale significantly affects shale gas content and its seepage capacity.However,the mechanism of water adsorption by shale is still unclear due to its strong heterogeneity and complicated pore structure.The relationship between the adsorbed water content at different relative humidities(RHs)and shale compositions,as well as shale pore structure and the spatial configuration relationship between organic matter(OM)and clay minerals,was investigated to clarify the controlling factors and mechanisms of water adsorption by Longmaxi Formation shale from the Southern Sichuan Basin in China.Consequently,the water adsorption process could be generally divided into three different stages from 0%RH to 99%RH.Furthermore,the Johnston’s clay mine ral interlayer pore structure model(JCM),the Freundlich model(FM)and the Dubinin-Astakhov model(DAM)were tested to fit the three water adsorption stages from low RH to high RH,respectively.The fitting results of the JCM and FM at lower RHs were far from good,while the fitting results of DAM at higher RHs were acceptable.Accordingly,two revised models(LRHM and MRHM)considering the spatial configuration relationship between OM and clay minerals were proposed for the two stages with lower RHs,and performed better fitting results indicating the pronounced effect of the spatial configuration relationship between OM and clay minerals on the water adsorption process of Longmaxi Formation shale.The outcomes of this study will contribute to clarifying the water distribution characteristics in the pore network of shale samples with variable water contents.

Methane Adsorption Capacity Reduction Process of Water-Bearing Shale Samples and Its Influencing Factors: One Example of Silurian Longmaxi Formation Shale from the Southern Sichuan Basin in China

Due to the existence of water content in shale reservoir,it is quite meaningful to clarify the effect of water content on the methane adsorption capacity(MAC)of shale.However,the role of spatial configuration relationship between organic matter(OM)and clay minerals in the MAC reduction process is still unclear.The Silurian Longmaxi Formation shale samples from the Southern Sichuan Basin in China were prepared at five relative humidity(RH)conditions(0%,16%,41%,76%,99%)and the methane adsorption experiments were conducted on these water-bearing shale samples to clarify the MAC reduction process considering the spatial configuration relationship between clay minerals and OM and establish the empirical model to fit the stages.Total organic carbon(TOC)content and mineral compositions were analyzed and the pore structures of these shale samples were characterized by field-emission scanning electron microscopy(FE-SEM),N2 adsorption and high-pressure mercury intrusion porosimetry(HPMIP).The results showed that the MAC reduction of clay minerals in OM occurred at different RH conditions from that of clay minerals outside OM.Furthermore,the amount of MAC reduction of shale samples prepared at the same RH condition was negatively related with clay content,which indicated the protection role of clay minerals for the MAC of water-bearing shale samples.The MAC reduction process was generally divided into three stages for siliceous and clayey shale samples.And the MAC of OM started to decline during stage(1)for calcareous shale sample mainly because water could enter OM pores more smoothly through hydrophobic pathway provided by carbonate minerals than through hydrophilic clay mineral pores.Overall,this study will contribute to improving the evaluation method of shale gas reserve.