Anhydrous Pyrolysis Research Articles

Micromechanical variation of organic matter (kerogen type I) under controlled thermal maturity progression

Shale formations have recently gained plenty of attention owing to their large amounts of reserves. Horizontal drilling and hydraulic fracturing are the proposed approaches for the development of shale formations. The extended information of the mechanical properties of shale formation is crucial for designing a successful hydraulic fracturing operation. On the other hand, the mechanical properties of such organic-rich formations are greatly affected by the mechanical characteristics of the present kerogen (organic matter), which dramatically changes during the maturation process. In this study, a Qingshankou shale sample containing kerogen type I is mechanically investigated at different maturity levels using the grid nanoindentation approach. To this end, the original immature sample is artificially matured during hydrous (HP) and anhydrous (AHP) pyrolysis. More than 930 nanoindentation tests were performed on grids of 9 × 8 on the surface of 13 samples with different maturities. The test results showed that the presence of water during pyrolysis can significantly affect the shale sample’s mechanical characteristics. In higher temperatures and higher levels of maturity, the role of water becomes more pronounced. During hydrous pyrolysis, kerogen produces larger amounts of oil and bitumen, which become progressively porous. While the original sample showed a Young’s modulus value of more than 48 GPa, and it fluctuated between approximately 19 and 32 GPa during the HP scenario and between 17 and 34 GPa during the AHP process. In terms of hardness, the original sample exhibited an initial value of about 1.1 GPa and more mature samples reflected hardness values in the range of approximately 0.3 and 0.97 GPa in both scenarios. According to the trends of mechanical properties during maturation, mechanical properties decreased at the initial stage of maturation and remained relatively constant during the oil window. Then, another decline was detected at the wet-gas window’s closure. In the dry-gas window, HP and AHP scenarios exhibited different behaviors mainly due to the chemical structure of the kerogen residue.

Generation Potential and Characteristics of Kerogen Cracking Gas of Over-Mature Shale

To investigate the characteristics and generation potential of gas generated from over-mature shale, hydrous and anhydrous pyrolysis experiments were carried out on the Longmaxi Formation in the Anwen 1 well of the Sichuan Basin of China at temperatures of 400–598 °C and pressures of 50 Mpa, with (hydrous) and without (anhydrous) the addition of liquid water. The results show that in the presence of water, the total yield of carbon-containing gases (i.e., the sum of methane, ethane, and carbon dioxide) was increased by up to 1.8 times when compared to the total yield from the anhydrous pyrolysis experiments. The increased yield of carbon dioxide and methane accounted for 89% and 10.5% of the total increased yield of carbon-containing gases. This indicated that the participation of water could have promoted the release of carbon from over-mature shale, like we used in this study. The methane generated in the hydrous pyrolysis experiments was heavier, with a δ13C value of −21.27‰ (544 °C) compared to that generated in the anhydrous pyrolysis experiments, which showed a lighter δ13C of −33.70‰ (544 °C). It is noteworthy that the δ13C values of the methane from hydrous pyrolysis at >500 °C were even heavier than that of the kerogen from the over-mature shale, although the δ13C values of the methane show an overall increasing trend with increasing temperature both in hydrous and anhydrous pyrolysis. The carbon dioxide from hydrous pyrolysis was less enriched in 13C relative to that from anhydrous pyrolysis. Specifically, the δ 13C values of the carbon dioxide increased with the increasing temperature in anhydrous pyrolysis, whereas they remained nearly constant with increasing temperature in hydrous pyrolysis. The overall lighter δ13C values of the carbon dioxide generated in the hydrous pyrolysis experiments likely indicate that water tends to prompt the release of lighter carbon and/or suppress the release of heavier carbon from over-mature shale in the form of carbon dioxide, especially at higher temperatures, for example, of >510 °C.

Artificial maturation of a Silurian hydrocarbon source rock: Effect of sample grain size and pyrolysis heating rate on oil generation and expulsion efficiency

Although artificial maturation of hydrocarbon source rocks by laboratory pyrolysis is far from representing natural maturation, it is a useful tool to investigate the process. In this study, we used routine open system pyrolysis for powder samples and Restricted System anhydrous Pyrolysis (RSP) for cm-sized Silurian shale source rock fragments to artificially mature the samples to different end-temperatures in the presence of a flowing carrier gas. Maturation experiments on rock fragments enable the simulation of physical barriers for the generated hydrocarbons that need to be overcome before expulsion from the source rock can occur. Based on the artificial maturation results in this study, oil expulsion efficiency from the Silurian shale source rock was 46% at the early oil generation stage and increased to 74% at approximately the peak oil generation stage.Furthermore, we have compared artificial maturation results from powder-form and fragment-form samples with natural-maturation series and found that artificial maturation of fragment-form samples sufficiently resembles natural maturation of the Silurian shales. It is therefore possible to simulate the early, middle and peak oil generation stages of natural maturation and expulsion efficiencies. This implies that, lab-based oil expulsion efficiencies from increasing maturity and hydrocarbon generation can be incorporated into the basin modeling.

Simulation of Thermal Maturity in Kerogen Type II Using Hydrous and Anhydrous Pyrolysis: A Case Study from the Bakken Shale, United States

Simulation of Thermal Maturity in Kerogen Type II Using Hydrous and Anhydrous Pyrolysis: A Case Study from the Bakken Shale, United States

Mechanism of water-induced alterations to nanoscale pores: Implications from anhydrous versus hydrous pyrolysis

In this study, shale samples from the Chang7 Member of Triassic Yanchang Formation in Ordos Basin, China were used to conduct artificially induced thermal maturity experiments from 250 °C to 450 °C for 72 h. The role of water in organic matter (OM) conversion and nanoscale porosity alterations were observed and discussed comprehensively by Rock-Eval pyrolysis, low pressure N2/CO2 adsorption, Fourier transform infrared spectroscopy (FTIR) and water-soluble organic acids (WSOAs) experiments. Results show that Rock-Eval pyrolysis parameters (Tmax, S1, and S2), TOC content, WSOAs and pore volume (PV) show slight changes below 350 °C while these parameters were considerably altered above 400 °C under two different pyrolysis conditions (anhydrous and hydrous), indicating that after 400 °C, the OM conversion and bitumen cracking will accelerate. In comparison to anhydrous pyrolysis, hydrous pyrolysis always has smaller Tmax, implying that water could inhibit OM thermal progression. Moreover, S1 of hydrous pyrolysis is approximately two times higher than that of anhydrous pyrolysis, which originates from water providing an exogenous source of hydrogen to generate excessive volumes of hydrocarbons, enhancing the conversion rate of OM. The WSOAs are 2 to 4 times greater under hydrous pyrolysis than anhydrous pyrolysis, denoting that the presence of water could improve the yield of organic acids via inhibiting the polycondensation of oxygen-containing functional groups and oxidizing organic components by hydroxyl radicals. Moreover, below 350 °C, pyrolysis shale residues exhibit a slightly smaller PV in hydrous pyrolysis, mainly due to the infilling effect of bitumen. However, exceeding 400 °C, PV that was obtained from low pressure N2 adsorption under hydrous pyrolysis conditions is found to be two times as large as the value under anhydrous pyrolysis conditions, which is attributed to the net-PV increase reactions such as thermal cracking, and the dissolution of organic acids. Furthermore, in anhydrous pyrolysis, the polycondensation of oxygen-containing functional groups and the carbon-carbon cross linking could be considered as the two main reaction pathways to release the sources of hydrogen. Collectively, the presence of water is significant for hydrocarbon generation and porosity evolution during thermal progression of OM at various stages.

Natural and laboratory-induced maturation of kerogen from the Vaca Muerta Formation: A comparison study

Artificial maturation of kerogen is a widely used technique to assess the hydrocarbon potential of shale rocks and to observe thermal transformations of organic matter in the laboratory. However, the degree of reproducibility of natural geological transformation at the molecular level is still not fully established. In the present work, a set of kerogens isolated from Vaca Muerta Formation core samples at varying levels of thermal maturity were studied. Another set of samples was obtained by anhydrous pyrolysis of kerogen in a closed system. Molecular structures measured by solid-state techniques (13C NMR, XPS and FTIR) were compared in natural and artificially matured samples at equivalent levels of thermal maturation. We observed that heating in an anhydrous closed system accurately reproduces most of the molecular structural changes observed during natural thermal maturation, with exceptions related to the branching degree and oxygen containing groups. The evolution of some parameters, such as N and S content, are highly variable in the natural samples because of differences in their deposition environments. In these cases, artificial thermal maturation changes are smaller and follow more clearly defined trends because variables other than thermal changes are not present. This is the first work comparing natural and artificial thermal maturation in the Vaca Muerta Formation and add valuable data regarding the limitation of artificial maturation that can be extrapolated to other formations.

Formation of volatile organic sulfur compounds by low thermal maturation of source rocks: A geochemical proxy for natural gas

Volatile organic sulfur compounds (VOSC) are trace components of natural gas that can provide substantial information regarding gas origins, migration, and key processes such as H2S generation and its occurrence in natural gas reservoirs. In the current study we demonstrate the applicability of VOSC as a proxy for gas-source rock correlations and identification of interactions between H2S and other natural gas components. We studied the molecular and isotopic compositions of VOSC formed during low-level thermal maturation (%Ro equivalent = 0.60–0.71) of six different immature source rocks covering a variety of kerogens (types I, II, II-S and III). Anhydrous pyrolysis experiments (300 °C, 72h) were performed on all the source rocks studied, and the produced gases were analyzed for their molecular compositions and compound specific sulfur isotopes of the various VOSC formed. The formed gases were either dominated by CH4 (32.2–49.9%) or CO2 (31.9–46.2%) and contained a variety of alkanes in the C2–C5 range. H2S formed in 6 out of 8 experiments at concentrations ranging from 0.6 to 4.3%. The results demonstrated formation of VOSC in all experiments, regardless of kerogen types or source rock lithologies. The formation of thiols (16–121.2 ppm) in the produced gas was restricted to those experiments that contained H2S. This indicates that thiols formation is limited to gas-phase interactions between H2S and hydrocarbons. In contrast, thiophenes formed in all experiments (14.9–1778.8 ppm) regardless of H2S presence. Thiols preserved the δ34S signal of their associated H2S due to gas-phase interactions between the two, while thiophenes showed no interaction with the associated H2S and instead preserved the δ34S signature of the bulk kerogen (within 3.5‰ on average) of each source rock. This work demonstrates the applicability of thiophenes to act as a gas-source rock proxy for natural gas and thiols as a proxy for identification of present or paleo-interactions between natural gas and H2S.

Pore structure characterization of solvent extracted shale containing kerogen type III during artificial maturation: Experiments and tree-based machine learning modeling

Shale samples with type III kerogen from the Damoguaihe formation were exposed to hydrous and anhydrous pyrolysis (HP and AHP) in the temperature range of 300–450 °C. Next, soluble organic matter (OM) and the liquid yield were removed from the pyrolyzates after each step of thermal maturation. N2 adsorption tests were performed to assess the pore structures of the samples. Furthermore, deconvolution and fractal dimension analyses were executed to unveil pore clusters and discern the complexity of the pore network within each sample. Finally, two tree-based machine learning algorithms, random forest (RF) and extra trees (ET) were applied to model the N2 adsorption/desorption data of pyrolyzates to predict pore structure variations. Based on the results, HP pyrolyzates had higher bitumen reflectance (BRo%) values than AHP ones at all temperature sequences, which confirms water controls thermal maturity. AHP pyrolyzates exhibited larger average pore diameters across all temperatures, while HP pyrolyzates displayed higher BET surface areas in contrast to AHP pyrolyzates. Also, the average pore diameter of HP pyrolyzates with soluble OM and liquid yield extracted did not change significantly during thermal maturation, while the average pore diameter of AHP ones increased, peaking at 400 °C in post-mature stage. The largest total pore volume of HP samples was observed at the end of the wet gas window, while this was observed for AHP samples in the dry gas window. Three mesopore and four macropore clusters were identified in the original sample. Moreover, pore clusters of the pyrolyzates underwent diverse changes during thermal maturation, without following a specific trend, influenced by both temperature and pyrolysis conditions. Abundance of micropores, finer mesopores (2–10 nm), and a smaller average pore diameter in HP pyrolyzates compared to the AHP is the main reason for the higher fractal dimensions showing a more complex pore structure and/or rougher pore surface. Intelligence modeling exhibited that RF outperformed ET in estimating N2 adsorbed/desorbed volumes for the samples. Ultimately, sensitivity analysis revealed that water exerted a more significant influence on pore development in shales during thermal progression, outweighing the impact of temperature.

Experimental investigation and intelligent modeling of pore structure changes in type III kerogen-rich shale artificially matured by hydrous and anhydrous pyrolysis

The occurrence and enrichment of shale plays are highly controlled by pore characteristics of the formation. In this study, an immature sample rich in kerogen type III from the Damoguaihe formation, Hailar Basin in China is subjected to hydrous and anhydrous pyrolysis (HP and AHP) across an extensive temperature range (300–450 °C). Next, low-pressure N2 adsorption analysis was conducted on the pyrolyzate of each maturity stage to study the pore structures’ evolution during thermal maturity simulation. Moreover, deconvolution and fractal dimension analyses were implemented to study pore families and the complexity of pores within the shale samples. Finally, radial basis function (RBF) neural networks optimized by four evolutionary approaches were applied for modeling N2 adsorption data obtained from the HP and AHP samples. According to the results, the original shale sample and all pyrolyzates obtained with HP and AHP scenarios exhibited type IV isotherm with H3 hysteresis loops. As a whole, BET surface area, micro-, meso- and total pore volume of HP pyrolyzates were higher than AHP ones. The unheated shale sample had seven families containing three mesopore and four macropore groups. Although all pyrolyzates obtained from the pyrolysis had families with similar means, their pore volumes were entirely different, which proves that the pore structure of samples undergoes changes during thermal maturation and the presence of water can also enforce these changes. Both fractal dimensions showed a direct relationship with BET surface area and a negative correlation with the average pore diameter of shale samples. The RBF model optimized by differential evolution (DE) delivered a mean absolute percent relative error (MAPRE) value of 4.84% and determination coefficient (R2) of 0.9946 for the total data set, which outperforms other RBF models in predicting N2 adsorption/desorption tests of pyrolyzates. The outcome of sensitivity analysis suggested that the N2 adsorption/desorption behavior of the pyrolyzates was mostly affected by relative pressure and the pyrolysis type (HP or AHP). Ultimately, the results clearly revealed that the effect of water on the pores' alteration of shales with type III kerogen is greater than the effect of temperature or thermal maturity itself.

Pore structure evolution of Qingshankou shale (kerogen type I) during artificial maturation via hydrous and anhydrous pyrolysis: Experimental study and intelligent modeling

In this study, alterations in the pore structure of the Qingshankou shale during hydrous and anhydrous pyrolysis (HP and AHP) over wide ranges of temperature (300–450 °C) were studied to elucidate the role of water. Mineralogy of the original shale sample along with geochemical properties and pore structure after each step of artificial thermal maturation were analyzed using X-ray diffraction (XRD), Rock-Eval pyrolysis, and N2 adsorption, respectively. Complexity of pore structure was assessed via fractal dimension analysis followed by delineating different pore families in the samples' PSD curves. Next, four common artificial neural networks (ANNs) models were implemented along with Bayesian regularization (BR) and Levenberg-Marquardt (LM) optimization algorithms to model the N2 adsorption/desorption volume as thermal maturity progressed. Results showed that all samples represent Type IV hysteresis loop while the amount of N2 adsorption during HP was much higher than that of the AHP revealing the importance of water. Overall, the complexity of AHP samples’ pore structure was less than that of the HP since the count of pores with smaller pore width was reduced more during thermal progression. Deconvolution analysis showed that the original sample has eight pore families (7 in mesopore and 1 in the macropore range), while pore families with larger mean pore width were formed and expanded and pore families with smaller mean pore width were eliminated as thermal maturation progressed in both HP and AHP. Moreover, the average absolute percent relative error (AAPRE) of 3.74% for the entire data inferred that generalized regression neural network (GRNN) model was superior for the estimation of N2 volume adsorbed and desorbed. Finally, sensitivity analysis revealed that the relative pressure and pyrolysis method (AHP or HP) respectively had the strongest linear and non-linear relationships with the N2 adsorption/desorption volume. Collectively, this case confirmed the role that water plays in the evolution of pore structures throughout thermal maturation, which could be even more significant than temperature.

Differential effects of clay mineralogy on thermal maturation of sedimentary n-alkanes

Clay minerals serve as important catalysts for the degradation of a range of biomolecules during diagenesis, yet their effects are seldom considered when interpreting organic molecular and isotopic data in the context of paleoenvironmental reconstruction. We investigated the thermal maturation of immature sedimentary organic matter in the presence of two clay minerals (kaolinite and montmorillonite) using a series of laboratory-based anhydrous pyrolysis experiments. Organic matter was extracted from a modern terrestrial sediment, mixed with each clay mineral, and heated at 100–300 °C for up to 30 days – in this way, initial organic matter was identical in each system. Abundances, molecular distributions, and paired compound-specific stable isotopic compositions (δDn-alkane and δ13Cn-alkane) of n-alkanes were measured as a function of heating time. For both kaolinite and montmorillonite amended experiments, the shifts in molecular distributions are highly controlled by significant secondary production of n-alkanes from molecularly large lipid precursors, as evidenced by significant increases in the total amount of n-alkanes accompanying increased thermal maturation. Significant decreases in carbon preference index (CPI) are observed before minor decreases in average chain length (ACL), leading to behavior in CPI-ACL space that is fundamentally different from identical systems free of clay minerals. Furthermore, distinct distributions of secondary n-alkanes between the clay mineral systems indicate differential mechanisms and sites of precursor degradation. In the presence of clay minerals, δ13Cn-alkane of immature bituminous organics initially decreases with increasing thermal maturation, opposite most data reported from experimental alteration of relatively mature sedimentary matter. This shift is similarly driven by secondary production of n-alkanes, arising from kinetic fractionation associated with preferential cleavage of 12C12C bonds from parent molecules – the kinetics of this process vary per clay mineralogy but are controlled by the same process. Conversely, we see an enrichment in δDn-alkane with increasing maturation, indicating control of the two isotopic systems by separate mechanisms. Moreover, kaolinite and montmorillonite exhibit differential control on δDn-alkane, leading to separate domains in dual isotopic space. Overall, the changes in δ13Cn-alkane and δDn-alkane are relatively small over the timescales studied, even at temperatures as high as 300 °C (less than ∼0.6–1‰ for δ13Cn-alkane and ∼8–15‰ for δDn-alkane). Considering these factors on a geological timescale, variations in clay mineralogy through a buried sedimentary sequence may impart matrix effects on molecular and isotopic signatures that can bias interpretation of paleoenvironmental conditions.

Comparison of Change in Nanopore Structure of Oil Shale after Anhydrous and Sub/Supercritical Water Pyrolysis

Oil shale is an important part of unconventional resources, which is considered as an important replacement for traditional oil resources. At present, the underground in-situ conversion method of oil shale is mainly aimed at shallow reservoirs, and it is difficult to apply to in-situ exploitation of oil shale with a depth of more than 1000m. In view of the portability, fracturing and extraction characteristics of high-pressure sub/supercritical water, it has become the research direction of in-situ mining of deep oil shale. The evolution of pore structure of oil shale is the basis for exploring the production mechanism of sub/supercritical water pyrolysis of oil and gas, which has important theoretical and scientific significance for improving the development and utilization of in-situ injection of sub/supercritical water in deep oil shale. Therefore, in this paper, the oil shale of Jijuntun Formation of Paleogene in Fushun Basin is taken as the research object. The pyrolysis experiments of oil shale in three ways, namely, water-free (electric heating), subcritical water and supercritical water, are carried out by means of high temperature and high-pressure source rock pyrolysis simulation device. The evolution characteristics of nano-pore structure under different pyrolysis methods are studied by XRD and low temperature nitrogen adsorption technology. The results show that, compared with anhydrous pyrolysis at the same temperature, the pore size of 3-30 nm of oil shale increases significantly after sub/supercritical water pyrolysis. The phenomenon of kaolinite illite fossilization increases, and the overall weak acidic environment is more conducive to the transformation of illite into Illite and montmorillonite mixed layer minerals, easier to increase the pore space in oil shale, and conducive to the migration and accumulation of produced oil and gas.

Effect of thermal maturation on the isotopic compositions of volatile organic sulfur compounds released from a kerogen by hydrous and anhydrous pyrolysis

Volatile organic sulfur compounds (VOSCs) may provide an alternative and improved approach in the evaluation of source and thermal maturity of natural gas. However, the role of water in the generation and decomposition of VOSCs is still ambiguous. Hydrous pyrolysis experiments were conducted on the isolated type Ⅱ-S kerogen of a source rock collected from the Ghareb Formation, Israel at 200–360 ℃ for 72 h (Easy%Ro = 0.32–1.20). The evolved gases were quantified for C1-C5 hydrocarbons, CO2, H2S and VOSCs. Compound specific isotope analysis were conducted both on the VOSCs and H2S (δ34S), and also on the C1-C5 hydrocarbons and CO2 (δ13C, δ2H). The results show that thiols concentration increased from 200 ℃ to 300 ℃ and then decreased from 300 ℃ to 360 ℃. The formed thiols isotopically co-vary with H2S from 200 ℃ to 340 ℃ and present the opposite trend with H2S from 340 ℃ to 360 ℃. The δ34S values of thiols are usually 3–7‰ lighter than the parent kerogen and 0.5–4‰ heavier than H2S. The concentrations of thiophenes generally increased with thermal stress with peak generation at 360 ℃, the δ34S values of thiophenes are mostly < 2–4‰ lighter than the parent kerogen and 2–8‰ heavier than H2S through the experiments. The δ13C and δ2H values of gaseous hydrocarbons are gradually enriched in heavy isotopes with increased thermal maturity. VOSCs dominated by thiols and thiophenes are generated by two ways: 1. the interactions between H2S and hydrocarbon molecules (synthetic pathway), 2. thermal cracking of OMs including kerogen and associated bitumen primary cracking and hydrocarbon secondary cracking (thermal cracking pathway). The synthetic pathway played the major role in the generation of thiols at the immature and early mature stages (200–300 ℃, Easy%Ro = 0.32–0.71), the cracking pathway has the dominant effect on the occurrence of thiols at higher thermal maturity levels (300–360 ℃, Easy%Ro = 0.71–1.20). The main pathway of thiophenes formation throughout the experiments is by the thermal cracking pathway. In the hydrous experiments, water promotes the synthetic pathway that generated thiols and retarded the thermal cracking pathway that forms thiophenes, but had no significant impact on δ34S values of individual VOSCs, δ13C and δ2H values of gaseous hydrocarbons. Therefore, combining with carbon and hydrogen isotopic compositions of gaseous hydrocarbons, molecular and sulfur isotopic compositions of individual VOSCs in the gas phase can provide valuable clues for petroleum systems in sedimentary basins including gas sources, generation pathways, thermal maturity levels and petroleum secondary transformations, such as thermochemical sulfate reduction in the subsurface reservoirs.

Effect of Clay Minerals and Rock Fabric on Hydrocarbon Generation and Retention by Thermal Pyrolysis of Maoming Oil Shale

In traditional kerogen pyrolysis experiments, the effects of minerals and rock fabric on the pyrolysis products were ignored. To further clarify the role of the mineral matrix and rock fabric on hydrocarbon generation and retention, a closed anhydrous pyrolysis experiment was conducted on core plugs, powdered rock and kerogen from a clay-rich sample of Maoming oil shale within a temperature range of 312 °C to 600 °C, at a fixed pressure of 30 Mpa. The experiment’s results showed that the yields of heavy hydrocarbons (C14+) generated from the core plugs and powdered rock were obviously lower than that of kerogen, which may be caused by the retention effect of clay minerals in raw shale. The yields of gaseous hydrocarbons generated from core plugs were lower compared with powdered rock due to the retention of C2+ hydrocarbons by the intact rock fabric and the preferential generation of methane. Light hydrocarbon (C6-14) yields generated from the core plugs and powdered rock were higher than kerogen, which may be the consequence of the cleavage of extraction bitumen and the interactions with kerogen. Moreover, the ratios of iso to normal paraffin (iC4/nC4, iC5/nC5) of the core plugs and powdered rock were higher than kerogen. Our experimental results show that kerogen pyrolysis in a confined system may overestimate the hydrocarbon generation potential due to the negligence of the retention effect of minerals and the rock fabric, especially in the source rocks rich in clay minerals.

Physico-chemical variations of shale with artificial maturation: In the presence and absence of water

Pyrolysis is widely employed to simulate the oil generation process in the lab. This method has been used so far to study systematic evolution of pore structures or geochemical properties of source rocks during thermal maturation. Although the importance, variations in mechanical properties of shale samples during the pyrolysis which plays important role in unconventional reservoir development are rarely studied. Herein, we combined grid nanoindentation method with gas adsorption, organic petrology and bulk geochemical analysis to evaluate changes in mechanical properties of shale samples under anhydrous pyrolysis (AHP) and hydrous pyrolysis (HP). The results showed that thermal maturity (%BRo) of the products is different under these two separate pyrolysis methods. Moreover, at the same pyrolysis temperature, mechanical parameters (i.e., Young's modulus, hardness, and fracture toughness) of the HP product were found to be smaller than those of the AHP product. During the pyrolysis (temperature from 300 to 450 °C), the reduction in the mechanical parameters (mean Young's modulus, mean hardness, and mean fracture toughness) following AHP and HP are more than 40%, which must be considered in the development of unconventional reservoirs where mechanical parameters are critical for successful field operations. Most importantly, this study confirmed that water is a significant factor in physico-chemical parameters of the pyrolyzates, which should be considered in the development plans of the formations that will undergo in situ conversion.

Evolution of porosity in kerogen type I during hydrous and anhydrous pyrolysis: Experimental study, mechanistic understanding, and model development

In this study, to clarify the role of water during thermal maturation on organic porosity evolution, pore structure characteristics of the Qingshankou shale (type I kerogen) were studied during anhydrous and hydrous pyrolysis (AHP and HP) over wide a range of temperature (300–450 °C). Following each step of thermal maturation, geochemical properties, and pore structure were analyzed with Rock Eval and low-pressure N2 adsorption, respectively. Furthermore, the deconvolution technique was applied to the pore size distribution curves to investigate different pore families and their complexity was assessed using fractal dimension analysis. Next, the volume of N2 adsorbed/desorbed was modeled using several intelligent models. It was found that organic matter displayed Type IV isotherm with hysteresis loops and mesopores stood out as the prevailing type of pores within the samples. Moreover, total surface area and pore volume were found less for AHP samples than the HP samples at all temperatures, which revealed the role of water in the evolution of organic porosity. Pore diameter in AHP samples was larger compared to HP ones, while the diameter of pores increased with the progress of thermal advance in both scenarios. The original sample exhibited five mesopore and two macropore families, while with rising temperature pore families with smaller average pore widths were decreased, and pore families with larger average pore widths were created and expanded. Furthermore, heterogeneity of the pores with maturation was more evident in AHP samples due to the decrease in the number of pores with smaller pore widths. The role of water in the creation of fractures within pyrobitumen was remarkable since it caused a substantial increase in the total pore volume of the organic matter during the gas window. Finally, modeling outcomes showed that cascade forward neural network (CFNN) outperformed other models in predictions of N2 volume adsorbed/desorbed with an average absolute percent relative error (AAPRE) of 2.48 %. It was understood that relative pressure followed by pyrolysis method (AHP or HP) were the most important variables in the estimation of N2 adsorbed/desorbed volumes based on sensitivity analysis. Collectively, the role of water on organic porosity evolution was confirmed based on distinct discrepancies in the two groups of samples pore structure details.

Mercury loss and isotope fractionation during thermal maturation of organic-rich mudrocks

Mercury (Hg) concentration and isotopic composition of organic-rich sedimentary rocks have been widely used as proxies to track ancient volcanism and associated environmental perturbations. However, interpretation of the Hg data is based on the assumption that the thermal maturity of the sedimentary rocks has limited effects on Hg abundance and isotopic composition, which is yet to be evaluated. Here we conduct closed-system anhydrous pyrolysis experiments to investigate the changes of Hg concentration and isotope composition during the thermal mature process, using both marine and lacustrine mudrocks. A siliceous shale section (Luocun, China) with heterogeneous thermal maturity caused by dike intrusion was also analyzed for Hg. Significant Hg loss (over 80%), with variations of δ202Hg (by 0.3 to 0.7‰) but small variations of Δ199Hg (by <0.1 to 0.36‰), were observed during the experiment. The Hg isotopic variation may be caused by the release of isotopically distinct Hg in different mineral phases at different temperatures. Samples from the Luocun section have anomalously low Hg and Hg/TOC values, due to thermal maturity. These findings suggest that (1) thermal maturation of organic-rich shales may be an important factor in distribution of Hg in sediments, and (2) the use of Hg, Hg/TOC and Hg isotopes proxies for paleoclimate and paleoceanography reconstruction should be applied in caution in substrates that may have experienced significant thermal alteration, especially if sill/dike intrusions were present that may cause large varieties of thermal maturity within sedimentary sections.

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

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 min 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.

Comparative study on the pyrolysis behavior and pyrolysate characteristics of Fushun oil shale during anhydrous pyrolysis and sub/supercritical water pyrolysis.

Injected steam can be converted to the sub/supercritical state during the in situ exploitation of oil shale. Thus, the pyrolysis behavior and pyrolysate characteristic of Fushun oil shale during anhydrous pyrolysis and sub/supercritical water pyrolysis were fully compared. The results revealed that the discharged oil yields from sub/supercritical water pyrolysis were 5.44 and 14.33 times that from anhydrous pyrolysis at 360 °C and 450 °C, which was due to the extraction and driving effect of sub/supercritical water. Also, sub/supercritical water could facilitate the discharge and migration of shale oil from the pores and channels. The H2 and CO2 yields in sub/supercritical water pyrolysis were higher than that in anhydrous pyrolysis, resulting from the water–gas shift reaction. The component of shale oil was dominated by saturated hydrocarbons in anhydrous pyrolysis, which accounted for 50–65%. In contrast, a large amount of asphaltenes and resins was formed during pyrolysis in sub/supercritical water due to the solvent effect and weak thermal cracking. The shale oil from anhydrous pyrolysis was lighter than that from sub/supercritical water pyrolysis. Sub/supercritical water reduced the geochemical characteristic indices and lowered the hydrocarbon generation potential and maturity of solid residuals, which can be attributed to the fact that more organic matter was depolymerized and released. The pyrolysate characteristic of oil shale in sub/supercritical water pyrolysis was controlled by multiple mechanisms, including solvent and driving effect, chemical hydrogen-donation and acid–base catalysis.

Effects of inherent pyrite on hydrocarbon generation by thermal pyrolysis: An example of low maturity type-II kerogen from Alum shale formation, Sweden

To resolve the controversy of iron sulfide effect on hydrocarbon generation of kerogen, a confined anhydrous pyrolysis experiment was performed on an Alum kerogen before and after the removal of kerogen-associated inherent pyrite within a temperature range of 336 ℃ to 600 ℃ at 50 MPa. The effect of kerogen-associated inherent pyrite on hydrocarbon generation and the reaction mechanism were explored by comparing the results from pyrite-contained kerogen with pyrite-removed kerogen. The thermal transformation of pyrite into pyrrhotite gradually increased with increasing temperature, particularly in the range of 432 ℃ − 528 ℃, accompanied by the formation of nascent sulfur. The bitumen/heavy hydrocarbons (C14+) yield was lower in the pyrite-contained (imbedded) kerogen due to strong bonding interaction between pyrite and kerogen. The temperature of peak liquid hydrocarbon (C6-14) production in the pyrite-contained kerogen was nearly 50 ℃ lower than that of the pyrite-removed kerogen, indicating that inherent pyrite accelerated the generation of liquid hydrocarbons. The wet gas yield (∑C2-5) decreased significantly for the pyrite-contained kerogen above 432 ℃, caused by the hydrogen abstraction of additional nascent sulfur. Moreover, the presence of inherent pyrite significantly increased the iso- to normal paraffin ratios (iC4/nC4, iC5/nC5).