Search Results (234)

The increasing need for sustainable valorization of fossil-based and waste-derived materials has gained interest in converting complex organic matrices such as kerogen into valuable chemicals. This study explores a two-step oxidative strategy to decompose and valorize kerogen-rich oil shale, aiming to develop a locally based source of aliphatic dicarboxylic acids (DCAs). The method combines air oxidation with subsequent nitric acid treatment to enable selective breakdown of the organic structure under milder conditions. Air oxidation was conducted at 165–175 °C using 1% KOH as an alkaline promoter and 40 bar oxygen pressure (or alternatively 185 °C at 30 bar), targeting 30–40% carbon conversion. The resulting material was then subjected to nitric acid oxidation using an 8% HNO₃ solution. This approach yielded up to 23% DCAs, with pre-oxidation allowing a twofold reduction in acid dosage while maintaining efficiency. However, two-step oxidation was still accompanied by substantial degradation of the structure, resulting in elevated CO₂ formation, highlighting the need to balance conversion and carbon retention. The process offers a possible route for transforming solid fossil residues into useful chemical precursors and supports the advancement of regionally sourced, sustainable DCA production from unconventional raw materials. Full article

The Silurian marine shale in the Sichuan Basin is currently the main reservoir for shale gas reserves and production in China. This study investigates the reservoir evolution of the Silurian marine shale based on fractal dimension, quantifying the complexity and heterogeneity of the shale’s pore structure. Physical simulation experiments were conducted on field-collected shale samples, revealing the evolution of total organic carbon, mineral composition, porosity, and micro-fractures. The fractal dimension of shale pore was characterized using the Frenkel–Halsey–Hill and capillary bundle models. The relationships among shale components, porosity, and fractal dimensions were investigated through a correlation analysis and a principal component analysis. A comprehensive evolution model for porosity and micro-fractures was established. The evolution of mineral composition indicates a gradual increase in quartz content, accompanied by a decline in clay, feldspar, and carbonate minerals. The thermal evolution of organic matter is characterized by the formation of organic pores and shrinkage fractures on the surface of kerogen. Retained hydrocarbons undergo cracking in the late stages of thermal evolution, resulting in the formation of numerous nanometer-scale organic pores. The evolution of inorganic minerals is represented by compaction, dissolution, and the transformation of clay minerals. Throughout the simulation, porosity evolution exhibited distinct stages of rapid decline, notable increase, and relative stabilization. Both pore volume and specific surface area exhibit a trend of decreasing initially and then increasing during thermal evolution. However, pore volume slowly decreases after reaching its peak in the late overmature stage. Fractal dimensions derived from the Frenkel–Halsey–Hill model indicate that the surface roughness of pores (D1) in organic-rich shale is generally lower than the complexity of their internal structures (D2) across different maturity levels. Additionally, the average fractal dimension calculated based on the capillary bundle model is higher, suggesting that larger pores exhibit more complex structures. The correlation matrix indicates a co-evolution relationship between shale components and pore structure. Principal component analysis results show a close relationship between the porosity of inorganic pores, microfractures, and fractal dimension D2. The porosity of organic pores, the pore volume and specific surface area of the main pore size are closely related to fractal dimension D1. D1 serves as an indicator of pore development extent and characterizes the changes in components that are “consumed” or “generated” during the evolution process. Based on mineral composition, fractal dimensions, and pore structure evolution, a comprehensive model describing the evolution of pores and fractal dimensions in organic-rich shale was established. Full article

The present study focused on the Upper Cretaceous to Middle Miocene sequence in the Central Gulf of Suez, Egypt. The Upper Cretaceous to Middle Miocene sequence in the October field is thick and deeply buried, consisting mainly of brown limestone, chalk limestone, and reefal limestone intercalated with clastic shale. This study integrated various datasets, including total organic carbon (TOC), Rock-Eval pyrolysis, visual kerogen examination, vitrinite reflectance (%Ro), and bottom-hole temperature measurements. The main objective of this study is to delineate the source rock characteristics of these strata regarding organic richness, thermal maturity, kerogen type, timing of hydrocarbon transformation and generation. The Upper Cretaceous Brown Limestone Formation is represented by 135 samples from four wells and is considered to be a fair to excellent source rock, primarily containing type I and II kerogen. It is immature to early mature, generating oil with a low to intermediate level of hydrocarbon conversion. The Eocene Thebes Formation is represented by 105 samples from six wells and is considered to be a good to fair oil source rock with some potential for gas, primarily containing type II and II/III kerogen. Most samples are immature with a low level of hydrocarbon conversion while few are mature having an intermediate degree of hydrocarbon conversion. The Middle Miocene Lower Rudeis Formation is represented by 8 samples from two wells and considered to be a fair but immature source rock, primarily containing type III kerogen with a low level of conversion representing a potential source for gas. The Middle Miocene Belayim Formation is represented by 29 samples from three wells and is considered to be a poor to good source rock, primarily containing kerogen type II and III. Most samples are immature with a low level of hydrocarbon conversion while few are mature having an intermediate degree of hydrocarbon conversion. 1D basin model A-5 well shows that the Upper Cretaceous Brown Limestone source rock entered the early oil window at 39 Ma, progressed to the main oil window by 13 Ma, and remains in this stage today. The Eocene Thebes source rock began generating hydrocarbons at 21.3 Ma, advanced to the main oil window at 11 Ma, and has been in the late oil window since 1.6 Ma. The Middle Miocene Lower Rudeis source rock entered the early oil window at 12.6 Ma, transitioned to the main oil window at 5.7 Ma, where it remains active. In contrast, the Middle Miocene Belayim source rock has not yet reached the early oil window and remains immature, with values ranging from 0.00 to 0.55 % Ro. The transformation ratio plot shows that the Brown Limestone Formation began transforming into the Upper Cretaceous (73 Ma), reaching 29.84% by the Miocene (14.3 Ma). The Thebes Formation initiated transformation in the Late Eocene (52.3 Ma) and reached 6.42% by 16.4 Ma. The Lower Rudeis Formation began in the Middle Miocene (18.7 Ma), reaching 3.59% by 9.2 Ma. The Belayim Formation started its transformation at 11.2 Ma, reaching 0.63% by 6.8 Ma. Full article

Despite the shale revolution triggering global shale oil and gas exploration, our understanding of the sedimentary environments of deep-water organic-matter-rich shale remains unclear. The sedimentary environment and facies of some siliceous shales at the bottom of the Longmaxi Formation in the Weiyuan area of the Sichuan Basin, China, were therefore analyzed. Nano-resolution petrological characterization and genesis analysis of the siliceous shales studied were conducted using nano-resolution petrologic image datasets. We identified these siliceous shales as microbial mats formed by deep-water traction current sedimentation. The microbial mats’ formation and burial diagenesis processes were divided into seven stages. The silt-grade bioclastic carpet deposits initially, colonizing mud-grade siliceous microbes and forming the siliceous microbial mat. Subsequently, carbohydrate-rich microbes thrive in sediment voids, forming the carbohydrate-rich microbial mat. Additionally, SOM undergoes four stages of burial diagenesis process, progressing from kerogens to pre-oil bitumen generation and ultimately transforming into porous pyrobitumen and nonporous pyrobitumen. This study will improve the understanding of deep-water traction current sedimentation and has implications for guiding shale gas exploration and development. Full article

This study presents a comprehensive experimental evaluation of pure methane (CH₄) and carbon dioxide (CO₂) adsorption on organic-rich shale samples from the Cesar-Ranchería Basin, Colombia. Adsorption isotherms were measured at two temperatures (50 °C and 80 °C) and up to 3 MPa using a manometric method. The data were fitted using the Langmuir model. The samples exhibit high total organic carbon (TOC) contents, ranging from 33.44% to 69.63%, but surprisingly low BET surface areas (1–7 m²/g), an uncommon combination in shale systems. Despite these low surface areas, the samples showed notable adsorption capacities, particularly for CO₂, which consistently outperformed CH₄ across all conditions. Maximum CO₂ adsorption capacities reached up to 1.6 mol/kg, while CH₄ values peaked at 0.49 mol/kg. The Langmuir parameters reflect a stronger affinity and greater capacity for CO₂, supporting its potential role in enhanced gas recovery and CO₂ sequestration. These findings contribute to understanding gas–shale interactions in thermally immature and highly organic-rich formations and highlight the importance of mineralogy and organic matter characteristics beyond surface area alone. This work provides novel insights into the adsorption behavior of Colombian shales and serves as a valuable reference for future gas in-place estimations and shale reservoir evaluations in similar geological contexts. Full article

Gypsum and salt rocks have been proven to act as seals for abundant oil and gas reserves on a global scale, with significant potential for hydrocarbon preservation and evolution. Notably, the sedimentary dynamics of non-evaporitic gypsum in terrestrial half-graben basins remain underexplored, particularly regarding its genetic link to hydrocarbon accumulation in interbedded mudstones. This study is based on the Zhanhua Sag, in which thick-layered gypsum rocks with dark mudstone are deposited. The gypsum crystals show the intermittent deposition characteristics. The cumulative thickness of the gypsum-containing section reaches a maximum of over 110 m. The spatial distribution of gypsum thickness correlates strongly with the location of deep-seated faults. The strontium and sulfur isotopes of gypsum indicate deep hydrothermal fluids as mineral sources, and negative oxygen isotope excursions also suggest that gypsum layers precipitated in situ from hot brine. Total organic carbon and Rock-Eval data indicate that the deep-lake gypsum rock system has excellent hydrocarbon potential, especially in the mudstone interlayers. This study developed a depositional model of deep-lake gypsum rocks with thermal brine genesis in half-graben basins. The gypsum-bearing system is rich in mudstone interlayers. These gypsum–mudstone interbeds represent promising targets for shale oil exploration after the initial breakthrough during the extraction process. These insights provide a theoretical framework for understanding gypsum-related petroleum systems in half-graben basins across the globe, offering guidance for hydrocarbon exploration in analogous sedimentary environments. Full article

The pathways and mechanisms of primary hydrocarbon migration, which are still not well understood, are of great significance for evaluating both conventional and unconventional oil and gas resources, understanding the mechanisms of shale oil retention, and predicting sweet spots. To investigate the petrography, geochemistry, and pore systems of organic-rich mudstones and organic-lean sand-silt intervals in core samples from the Yanchang shale in the Ordos Basin, China, we conducted thin-section observation, X-ray diffraction, Rock-Eval pyrolysis, field emission scanning electron microscopy (FE-SEM), and porosity analysis. Sand-silt intervals are heterogeneously developed within the Yanchang shale. The petrology, mineral composition, geochemistry, type, and content of solid organic matter as well as the pore type, pore size, and porosity of these intervals differ significantly from those of mudstones. Compared with mudstones, sand-silt intervals typically have coarser detrital grain sizes, higher contents of quartz, feldspar, and migrated solid bitumen (MSB), larger pore sizes, higher porosity, and higher oil saturation index (OSI). In contrast, they have lower contents of clay minerals, total organic carbon (TOC), free liquid hydrocarbons (S₁), and total residual hydrocarbons (S₂). The sand-silt intervals in the Yanchang shale serve as both pathways for hydrocarbon primary migration and “micro reservoirs” for hydrocarbon storage. The interconnected inorganic and organic pore systems, organic matter networks, fractures, and sand-silt intervals form the hydrocarbons’ primary migration pathways within the Yanchang shale. A model for the primary migration of hydrocarbons within the Yanchang shale is proposed. Full article

Permian shale gas, a resource-rich energy source, has garnered significant attention in recent years regarding its organic matter enrichment characteristics. This study conducted detailed observations via scanning electron microscopy (SEM) and optical microscopy to clarify the differences in the types and assemblages of hydrocarbon-generating organisms across Permian shale formations in Northwestern Sichuan, as well as to determine the characteristics of organic matter sources. The types and combinations of hydrocarbon-generating organisms in the Gufeng Formation, Wujiaping Formation, and Dalong Formation in Northwestern Sichuan are systematically summarized. Based on this information, the primary sources of organic matter in the Permian shale were analyzed. Hydrocarbon-generating organisms in the Permian shales of the study area are predominantly acritarchs (a type of planktonic algae), followed by higher plants and green algae. In the Gufeng Formation, acritarchs constituted the vast majority of hydrocarbon-generating organisms, with smaller amounts of higher plants and green algae. At the bottom of the Wujiaping Formation, the relative acritarch content decreases significantly, while that of higher plants substantially increases. In the Dalong Formation, acritarchs regain dominance, and higher plants decline, resembling the Gufeng Formation in microorganism composition. The relative content of green algae shows minimal variation across all layers. Overall, the organic matter sources of Permian shale in the study area were mainly acritarchs (derived from planktonic algae), followed by green algae, and terrestrial higher plants. During the Gufeng Formation period, the sea level was relatively high. The Kaijiang–Liangping Trough in Northwestern Sichuan was generally a siliceous deep shelf. The main source of organic matter was aquatic planktonic algae, containing a small amount of terrigenous input. At the bottom of the Wujiaping Formation, the sea level was relatively low, resulting in the overall coastal marsh environment of the Kaijiang–Liangping Trough, which was characterized by mixed organic matter sources, due to an increase in terrigenous organic matter content. The sedimentary environment and organic matter sources of the Dalong Formation were similar to those of the Gufeng Formation. This research can provide a theoretical basis for exploration and development of Permian shale gas. Full article

The complexity of the pore system hindered our understanding of the storage and transport properties of organic-rich shales, which in turn brought challenges to the efficient exploration and development of shale oil and gas. This study, based on elemental, mineralogical, petrographic, and petrophysical approaches, attempts to reveal the pore structure and fractal characteristics of a suite of Permian shales collected from the northeastern Sichuan Basin, China. The results showed that meso-pores make up the main proportion of the total pore volume in the Permian shale in this study; most of the pore size distribution patterns for micro pores and meso-macropores are bimodal. Pores related to clay minerals, organic matter pores, and intragranular dissolution pores are the main storage spaces in these shales. In these samples, ink-bottle pores dominate, with some slit and wedge-shaped ones developed. The morphology of the pores in the studied shales is mainly ink-bottle pores, with some slit-shaped and wedge-shaped pores. The fractal dimension D₂ is greater than D₁, indicating that the homogeneity of pore space is stronger than that of the specific surface area. Quartz in Permian shales inhibits the development of macro- and mesopore spaces and enhances pore heterogeneity, while clay minerals facilitate the development of macro- and mesopore spaces and attenuate pore heterogeneity. The organic matter content shows a negative impact on the macropore volume due to the stripped occurrence and matrix filling. This study has a vital significance for current exploration and development of shale gas in Permian strata in the Sichuan Basin and offers insights for Permian shales in other basins all over the world. Full article

The production of gas and condensate from liquid-rich shale reservoirs, particularly within heterogeneous lacustrine systems, remains a critical challenge in unconventional hydrocarbon exploration due to intricate multiphase hydrocarbon partitioning, including gases (C₁–C₂), volatile liquids (C₃–C₇), and heavier liquids (C₇₊). This study investigates a 120-meter-thick interval dominated by lacustrine deposits from the Lower Cretaceous Shahezi Formation (K₁sh) in the Songliao Basin. This interval, characterized by high clay mineral content and silicate–pyrite laminations, was examined to identify the factors controlling hybrid shale gas condensate systems. We proposed the Hybrid Shale Condensate Index (HSCI), defined as the molar ratios of (C₁–C₇)/C₇₊, to categorize fluid phases and address shortcomings in traditional GOR/API ratios. Over 1000 samples were treated by geochemical pyrolysis logging, X-ray fluorescence (XRF) spectrum element logging, SEM-based automated mineralogy, and in situ gas desorption, revealing four primary controls: (1) Thermal maturity thresholds. Mature to highly mature shales exhibit peak condensate production and the highest total gas content (TGC), with maximum gaseous and liquid hydrocarbons at T_max = 490 °C. (2) Lithofacies assemblage. Argillaceous shales rich in mixed carbonate and clay minerals exhibit an intergranular porosity of 4.8 ± 1.2% and store 83 ± 7% of gas in intercrystalline pore spaces. (3) Paleoenvironmental settings. Conditions such as humid climate, saline water geochemistry, anoxic bottom waters, and significant input of volcanic materials promoted organic carbon accumulation (TOC reaching up to 5.2 wt%) and the preservation of organic-rich lamination. (4) Laminae and fracture systems. Silicate laminae account for 78% of total pore space, and pyrite laminations form interconnected pore networks conducive to gas storage. These findings delineate the “sweet spots” for unconventional hydrocarbon reservoirs, thereby enhancing exploration for gas condensate in lacustrine shale systems. Full article

The third member of the Shahejie Formation (Es₃) in Dongying Sag is noteworthy for its abundance of laminated shale, considerable thickness, and high organic matter content, with carbonate interbeds playing a crucial role in reservoir properties. The salinity and pH of water influence the change of sedimentary environment and the mineral composition of sediment, thereby affecting the distribution characteristics of carbonate interbeds. Based on geochemical data from 8721 samples in the Dongying Sag, this study systematically analyzed the salinity and pH characteristics. This study is the first to develop an environmental zoning framework based on aqueous medium characteristics of aqueous media, and the favorable shale oil enrichment areas in Es₃ were identified by integrating carbonate mineral content analysis. The results showed that the lower part of Es₃ is dominated by a zone with high salinity–middle pH, and middle salinity–high pH with rich carbonate. Combining the development of carbonate interbeds, it is speculated that the sweet spots in Es₃ are high salinity–middle pH and middle salinity–high pH. The favorable areas are concentrated in the lower part of Es₃, including the western and northeastern parts of the Lijin Sub-Sag and the northern gentle slope of Guangrao. It provides a novel perspective on shale oil exploration through lacustrine environmental zonation. Full article

The lower and middle Carboniferous shale sequences are one of the important potential hydrocarbon source rocks in the piedmont of the southwestern Tarim Basin, China (PSTB). Rock samples were collected from the lower and middle Carboniferous formations on the Kushanhe, Altash, and Aitegou outcrops in the PSTB with the intention of mapping the hydrocarbon molecules within these shale sources and disclosing the relevant geochemical implications. The ratios of Pr/Ph < 1.0 and DBT/P < 0.4 and the enrichment of C₂₃ tricyclic terpanoid indicate that the Carboniferous shale sources were deposited in a reducing and sulfate-poor marine setting with the contribution of terrestrial freshwater. Marine aquatic algae act as the major contributor, resulting in the formation of Type II₁ kerogen. The Carboniferous shale sequences contain abundant diamondoids with 2–4 cages with the predominance of methyldiamantanes, dimethyldiamantanes, and methyltriamantanes. Quantitative extended diamondoid analysis indicates the occurrence of carbonate-rich and carbonate-poor organic facies in the PSTB. Compared to the carbonate-poor facies, the carbonate-rich facies is relatively depleted in C₂₇ diasteranes and rich in gammacerane, C₂₇ regular steranes, and alkylated triamantanes. This indicates that it was deposited in the more salty and stratified water column but with less input of land higher plants. The clay catalysis effects are assumed to be responsible for the discrepancy in steranes and diamondoids. The Carboniferous shale sequences also contain abundant polycyclic aromatic hydrocarbons with 2–5 rings with the predominance of C_0–1-phenanthrenes, chrysenes, and benzofluoranthenes. Thermal maturity parameters associated with polycyclic aromatic hydrocarbons and diamondoids suggest that the Carboniferous shale sources have arrived at the late mature to highly mature stage. This study provides the detailed molecular fingerprints of the lower and middle Carboniferous shale source sequences and explores the underlying geochemical implications. This should be helpful for oil–oil and oil–source correlations and hence petroleum exploration activity in the PSTB. Full article

Highly over-mature marine shales are distributed worldwide with substantial resource potential, yet their pore structure characteristics and controlling mechanisms remain poorly understood, hindering accurate shale gas resource prediction and efficient development. This study focuses on the Cambrian Niutitang Formation shales in the Upper Yangtze region of South China. To decipher the multiscale pore network architecture and its genetic constraints, we employ scanning electron microscopy (SEM) pore extraction and fluid intrusion methods (CO₂ and N₂ adsorption, and high-pressure mercury intrusion porosimetry) to systematically characterize pore structures in these reservoirs. The results demonstrate that the shales exhibit high TOC contents (average 4.78%) and high thermal maturity (average Ro 3.64%). Three dominant pore types were identified: organic pores, intragranular pores, and intergranular pores. Organic pores are sparsely developed with diameters predominantly below 50 nm, displaying honeycomb, slit-like, or linear morphologies. Intragranular pores are primarily feldspar dissolution voids, while intergranular pores exhibit triangular or polygonal shapes with larger particle sizes. CO₂ adsorption isotherms (Type I) and low-temperature N₂ adsorption curves (H3-H4 hysteresis) indicate wedge-shaped and slit-like pores, with pore size distributions concentrated in the 0.5–50 nm range, showing strong heterogeneity. Pore structure shows weak correlations with TOC and quartz content but a strong correlation with feldspar abundance. This pattern arises from hydrocarbon generation exhaustion and graphitization-enhanced organic pore collapse under high compaction stress, which reduces pore preservation capacity. The aulacogen tectonic setting engenders proximal sediment provenance regimes that preferentially preserve labile minerals such as feldspars. This geological configuration establishes optimal diagenetic conditions for the subsequent development of meso- and macro-scale of dissolution pores. Our findings demonstrate that feldspar-rich shales, formed in a proximal depositional system with well-developed inorganic pores, serve as favorable reservoirs for the exploration of highly over-mature marine shale gas. Full article

The most organic-rich shales are defined in the Dobele Fm. of the Aeronian Stage of about 10 m thick in west Lithuania. This particular layer is documented in the whole Baltic Basin. Compatible shales are widely distributed in other basins referred to as similar Silurian “hot” shales. The average TOC was estimated at 6.67 wt.% (good and excellent source rock). The thermal maturity of shales was evaluated through organic geochemical techniques, including TOC determination, Rock–Eval pyrolysis, and organic petrography studies. The thermal maturity varies from T_max = 431 °C and eq.VR_o = 0.65% (early oil) to T_max = 468 °C and VR_o = 1.38% (locally up to 1.94%) (late oil and wet to dry gas generation). It is notable, most of the study area is confined to regional-scale West Lithuanian Geothermal Anomaly. Most of the geothermal features, both palaeo- and recent, recorded in lateral variation in thermal maturity of shales unravel persistence of heat flow. Locally, the Variscan tectonic activity was imprinted in thermal maturity of organic matter-rich shales (Žemaičių Naumiestis anomaly). Full article

The Wufeng–Longmaxi formations in the Sichuan Basin have emerged as China’s principal shale gas exploration target, with drilling results confirming substantial resource potential. Although the Neijiang–Rongchang Block demonstrates promising production, significant performance variations among lithofacies and reservoir types highlight the need for enhanced understanding of reservoir evolution. This study integrates petrological analyses, SEM imaging, XRD characterization, seismic interpretation, and production data from multiple wells targeting the Wufeng–Long 1-1 Sub-member. Key insights reveal the following: (1) reservoir lithology consists predominantly of siliceous shale (68% occurrence), characterized by high quartz content (48% avg), low carbonates (<15%), and low clay (<30%); (2) organic-rich intervals contain Type I kerogen derived from planktonic algae, with thermal maturity indicating post-mature evolution; (3) premium reservoirs develop multi-scale pore networks combining organic-hosted pores, interparticle pores, and micro-fractures. Despite high brittle mineral content, mechanical competence decreases stratigraphically from the Wufeng Formation (78%) to Long 1-1⁷ (63%); (4) depositional redox conditions facilitated exceptional organic preservation. Core analyses reveal low porosity (5.5% avg) and ultra-low permeability (0.27 × 10⁻³ μm² avg), classifying reservoirs as multiple tight unconventional systems in the study area. The proposed lithofacies-controlled pore evolution model elucidates reservoir heterogeneity mechanisms, providing critical geological criteria for optimized shale gas development. Full article