Quantitative effect of kerogen type on the hydrocarbon generation potential of Paleogene lacustrine source rocks,Liaohe Western Depression,China

Kerogen types exert a decisive effect on the onset and capacity of hydrocarbon generation of source rocks.Lacustrine source rocks in the Liaohe Western Depression are characterized by thick deposition,high total organic carbon(TOC)content,various kerogen types,and a wide range of thermal maturity.Consequently,their hydrocarbon generation potential and resource estimation can be misinterpreted.In this study,geochemical tests,numerical analysis,hydrocarbon generation kinetics,and basin modeling were integrated to investigate the differential effects of kerogen types on the hydrocarbon generation potential of lacustrine source rocks.Optimized hydrocarbon generation and expulsion(HGE)models of different kerogen types were established quantitatively upon abundant Rock-Eval/TOC/vitrinite reflectance(R_(o))datasets.Three sets of good-excellent source rocks deposited in the fourth(Es4),third(Es3),and first(Es1)members of Paleogene Shahejie Formation,are predominantly types I-II_(1),II_(1)-II_(2),and II-III,respectively.The activation energy of types I-II_(2)kerogen is concentrated(180-230 kcal/mol),whereas that of type III kerogen is widely distributed(150-280 kcal/mol).The original hydrocarbon generation potentials of types I,II_(1),II_(2),and III kerogens are 790,510,270,and 85 mg/g TOC,respectively.The Ro values of the hydrocarbon generation threshold for type I-III source rocks gradually increase from 0.42%to 0.74%,and Ro values of the hydrocarbon expulsion threshold increase from 0.49%to 0.87%.Types I and II_(1)source rocks are characterized by earlier hydrocarbon generation,more rapid hydrocarbon expulsion,and narrower hydrocarbon generation windows than types II_(2)and III source rocks.The kerogen types also affect the HGE history and resource potential.Three types(conventional,tight,and shale oil/gas)and three levels(realistic,expected,and prospective)of hydrocarbon resources of different members in the Liaohe Western Depression are evaluated.Findings suggest that the Es3 member has considerable conventional and unconventional hydrocarbon resources.This study can quantitatively characterize the hydrocarbon generation potential of source rocks with different kerogen types,and facilitate a quick and accurate assessment of hydrocarbon resources,providing strategies for future oil and gas exploration.

Quantitative characterizations of anisotropic dynamic properties in organic-rich shale with different kerogen content

Understanding the quantitative responses of anisotropic dynamic properties in organic-rich shale with different kerogen content(KC)is of great significance in hydrocarbon exploration and development.Conducting controlled experiments with a single variable is challenging for natural shales due to their high variations in components,diagenesis conditions,or pore fluid.We employed the hot-pressing technique to construct 11 well-controlled artificial shale with varying KC.These artificial shale samples were successive machined into prismatic shape for ultrasonic measurements along different directions.Observations revealed bedding perpendicular P-wave velocities are more sensitive to the increasing KC than bedding paralleling velocities due to the preferential alignments of kerogen.All elastic stiffnesses except C_(13)are generally decreasing with the increasing KC,the variation of C_(1) and C_(33)on kerogen content are more sensitive than those of C_(44)and C_(66).Apparent dynamic mechanical parameters(v and E)were found to have linear correlation with the true ones from complete anisotropic equations independent of KC,which hold value towards the interpretation of well logs consistently across formations,Anisotropic mechanical parameters(ΔE and brittlenessΔB)tend to decrease with the reducing KC,withΔB showing great sensitivity to KC variations.In the range of low KC(<10%),the V_(P)/V_(S) ratio demonstrated a linearly negative correlation with KC,and the V_(P)/V_(S) ratio magnitude of less than 1.75may serve as a significant characterization for highly organic-rich(>10%)shale,compilation of data from natural organic rich-shales globally verified the similar systematic relationships that can be empirically used to predict the fraction of KC in shales.

Development review and the prospect of oil shale in-situ catalysis conversion technology

As an unconventional resource, oil shale possesses abundant reserves and significant potential for industrial applications. The rational and efficient development of oil shale resources holds immense importance in reducing national energy demand. In-situ catalytic technology, characterized by its high efficiency, low pollution, and minimal energy consumption, represents a key direction for future oil shale development. This paper provides a comprehensive review of research progress in in-situ oil shale mining technology, oil shale pyrolysis catalysts, the pyrolysis mechanism of kerogen, and the compatibility of different heating processes and catalysts. Furthermore, the paper proposes future research directions and prospects for oil shale in-situ catalytic technology, including reservoir modification, highefficiency catalyst synthesis, injection processes, and high-efficiency heating technology. These insights serve as valuable technical references for the advancement of oil shale in-situ catalytic technology.

Geochemical prerequisites for the formation of oil and gas accumulation zones in the South Turgay basin,Kazakhstan

This study predicts favorable oil and gas source-rock formation conditions in the Aryskum Depression of the South Turgay Basin,Kazakhstan.This study assesses the thermal maturity and characteristics of organic matter by determining its environmental conditions using data from geochemical analysis of core(pyrolysis)and oil(biomarkers and carbon isotopic compositions)samples.According to the geochemical parameters obtained by pyrolysis,the oil generation potential of the original rocks of most studied samples varies from poor to rich.The facies–genetic organic matter is predominantly humic and less frequently humus–sapropel,indicating organic matter accumulation in the studied samples were under moderately reducing conditions(kerogenⅢand Ⅱ types)and coastal–marine environments(kerogen typeⅠ).The carbon isotopic compositions of oils derived from the Jurassic deposits of the Aryskum Depression also indicate the sapropelic and mixed humic–sapropelic type of organic matter(kerogenⅡandⅠ).Biomarker analysis of oils indicates original organic matter formation in an anoxic environment.

Extractable and kerogen-bound hopanoids from typical Eocene oil shales in China

This study conducted a comparative analysis of extractable hopanoid hydrocarbons and those released via stepwise pyrolysis of typical Eocene immature oil shales in China,namely the Huadian,Maoming,and Fushun shales.Both the Huadian and Maoming shales exhibit immature indicators in extractable and kerogen-bound hopanoids(notably,high abundance of C_(29)to C_(32)17β,21β-hopanes and unsaturated hopenes).In contrast,the Fushun oil shale's hopanoids from extracts and pyrolyzates suggest a higher maturity level.The absence of neohopenes in the pyrolyzates of the shales underpins that the kerogenbound hopanoid skeletons resist rearrangement.However,the Huadian oil shale's asymmetric distribution of C_(29)and C_(30)hopenes and neohopenes hints at the presence of an additional source.Novel unsaturated hopenes,such as hop-20(21)-enes,identified in pyrolyzates of the three kerogens at various pyrolysis temperatures,reveal the occurrence of double bonds in kerogen-bound hopanoid skeletons without methyl rearrangements.The absence of hop-20-(21)-ene in extracts suggests that it might act as an intermediate of these novel hopenes during the epimerization of hopanoid skeletons within kerogen.The extractable and pyrolytic hopanoids'stereochemical alignment indicates that epimerization may occur in both ring systems and alkyl side chains of kerogen-bound hopanoid skeletons.Sequential stepwise pyrolysis proves to be a quick screening method for geological hopanoids without causing any significant alteration to the original skeletons even when cracking multiple covalent bonds is necessary.

Source rock potential assessment of the Huai Hin Lat Formation,Sap Phlu Basin, Nakhon Ratchasima Province, northeastern Thailand

The Huai Hin Lat Formation has a high-potential resource, and the Ban Nong Sai part was researched and sampled. To achieve this goal, petrographic analysis(kerogen types), geochemical analysis(total organic carbon content, TOC), vitrinite reflectance(Ro), and Rock–Eval(RE) pyrolysis were carried out in this study. According to the findings, types Ⅱ, Ⅲ, and Ⅳ were identified using a modified Van-Krevelen diagram because the higher mature source rock showing hydrogen index(HI) and oxygen index(OI) are continuously depleted and raised. However,microscopic observation describes macerals as primarily sapropelic amorphinite, therefore, type I is important. The TOC was determined to be between 1.90% and 7.06%,which is considered very good to excellent. The original total organic carbon(TOCo) was decided to use its maceral components to determine how to convert extremely mature TOC to TOCo. It varies between 5.13% and 10.74% and reaches a maximum of 57.21% which is comparable to TOC. At 0.82%–1.04%, 443–451 ℃, 0.50%–38.10%, and69.00%–99.59% are the vitrinite reflectance(Ro), maximum temperature(Tmax), production index(PI), and transformation ratio(TR), respectively. Late peak maturity refers to a mixture of oil and gas, whereas most TR ratios refer to the main gas phase. Similarly, the petroleum residual shows no indication of gas trapped at a volume of6309.50 mcf/ac-ft. In summary, source rock potential was assessed within a suitable risk range defined by Tmax(445.70 ℃), Ro(0.91%), TR(90.63%), TOC(8.15%),shale thickness(46 m), and kerogen type(type I).

Molecular insight into the oil displacement mechanism of CO_(2) flooding in the nanopores of shale oil reservoir

With the increasing demand for petroleum,shale oil with considerable reserves has become an important part of global oil resources.The shale oil reservoir has a large number of nanopores and a complicated mineral composition,and the effect of nanopore confinement and pore type usually makes the effective development of shale oil challenging.For a shale oil reservoir,CO_(2) flooding can effectively reduce the oil viscosity and improve the reservoir properties,which can thus improve the recovery performance.In this study,the method of non-equilibrium molecular dynamics(NEMD)simulation is used to simulate the CO_(2) flooding process in the nanoscale pores of shale oil reservoir.The performance difference between the organic kerogen slit nanopore and four types of inorganic nanopores is discussed.Thus,the effects of nanopore type and displacement velocity on the nanoscale displacement behavior of CO_(2) are analyzed.Results indicate that the CO_(2) flooding process of different inorganic pores is different.In comparison,the displacement efficiency of light oil components is higher,and the transport distance is longer.The intermolecular interaction can significantly affect the CO_(2) displacement behavior in nanopores.The CO_(2) displacement efficiency is shown as montmorillonite,feldspar>quartz>calcite>kerogen.On the other hand,it is found that a lower displacement velocity can benefit the miscibility process between alkane and CO_(2),which is conducive to the overall displacement process of CO_(2).The displacement efficiency can significantly decrease with the increase in displacement velocity.But once the displacement velocity is very high,the strong driving force can promote the alkane to move forward,and the displacement efficiency will recover slightly.This study further reveals the microscopic oil displacement mechanism of CO_(2) in shale nanopores,which is of great significance for the effective development of shale oil reservoirs by using the method of CO_(2) injection.

Distribution and geochemical significance of trace elements in kerogens from Ediacaran–Lower Cambrian strata in South China

Some trace elements(TEs),both bio-essential and redox-sensitive,are promising tracers of Earth’s surface processes.As an essential sedimentary organic matter,kerogen may have inherited and retained the key TEs from organisms.In this study,the distribution of TEs in kerogens from two sections(Dongkanshang and Fengtan) in South China was analyzed to explore its biogeochemical significance during Ediacaran-Lower Cambrian.Compared with V and Zn,the relative concentrations of Co,Ni,Cu,and Mo were generally higher in kerogens than in the whole rocks.Enrichment of TEs in the kerogen was involved in the selective utilization of TEs by different organic precursors and the competition of sulfide in the depositional environment.The significant content of TEs in the kerogens from deep-water facies corresponded to a more negative δ^(13) Ckeras a result of the dominant taxa of chemo autotrophs with tremendous bioaccumulation potential for trace metals and the reduction conditions favorable for organic matter preservation.Furthermore,the content variations of trace elements in the kerogens coincided with the rise and fall of the Ediacaran biota,implying that the trace elements might have played an important role in early life evolution.

Spectral narratives of microstructural restyling and their controls on hydrocarbon generation potential from coal

The low to medium-rank Tertiary coals from Meghalaya,India,are explored for the first time for their comprehensive micro-structural characterization using the FTIR and Raman spectroscopy.Further,results from these coals are compared with the Permian medium and high-rank coals to understand the microstructural restyling during coalification and its controls on hydrocarbon generation.The coal samples are grouped based on the mean random vitrinite reflectance values to record the transformations in spectral attributes with increasing coal rank.The aliphatic carbon and the apparent aromaticity respond sharply to the first coalification jump(R:0.50%)during low to medium-rank transition and anchizonal metamorphism of the high-rank coals.Moreover,the Raman band intensity ratio changes during the first coalification jump but remains invari-able in the medium-rank coals and turns subtle again during the onset of pregraphitization in high-rank coals,revealing a polynomial trend with the coal metamorphism.The Rock-Eval hydrogen index and genetic potential also decline sharply at the first coalification jump.Besides,an attempt to comprehend the coal microstructural controls on the hydrocarbon poten-tial reveals that the Tertiary coals comprise highly reactive aliphatic functionalities in the type I-S kerogen,along with the low paleotemperature(74.59-112.28℃)may signify their potential to generate early-mature hydrocarbons.However,the presence of type II-II admixed kerogen,a lesser abundance of reactive moieties,and overall moderate paleotemperature(91.93-142.52℃)of the Permian medium-rank coals may imply their mixed hydrocarbon potential.Meanwhile,anchizonal metamorphism,polycondensed aromatic microstructure,and high values of paleotemperature(~334.25 to~366.79℃)of the high-rank coals indicate a negligible potential of producing any hydrocarbons.

Geochemistry of Cretaceous Sea Rocks from the LEO-3X Well in the Eastern Abidjan Margin, Côte d’Ivoire Offshore Basin

In this study, we apply geochemical and statistical analyses to evaluate the source rocks and kerogen type of Cretaceous sediments from the Cote d’Ivoire sedimentary basin. The geochemical analysis includes pyrolysis data such as total organic carbon (TOC%), generation source potential (S2) and hydrogen index (HI). The results of the cluster analysis separated the source rocks in the study area into two main groups. 1) Source rocks characterized by HI > 300 (mg/g), TOC from 1.76% to 3.19% by weight, and S2 from 6.55 to 14.46 (mg/g), indicating good to excellent source rocks with type II kerogen and are capable of generating oil. 2) Source rocks characterized by HI between 200 and 300 (mg/g), TOC from 1.6 to 2.02 wt%, and S2 from 3.45 to 5.36 (mg/g) indicating medium to good source rocks with type II-III kerogen and capable of generating a mixture of oil and gas.

Hydrocarbon generation mechanism of lamalginite- and telalginite-dominated source rocks in a saline lake basin: A case study of the Permian Lucaogou formation in the Jimusaer Sag, Junggar Basin

The hydrocarbon generation of source rocks is significantly influenced by organic matter type, chemical element composition, and structural characteristics of kerogen. We classified the organic matter types in the shale of the Lucaogou Formation, Jimusar Sag, Junggar Basin, using organic petrology and rock pyrolysis as well as kerogen element and Fourier transform infrared (FT-IR) spectroscopy analyses, and compared the hydrocarbon generation mechanisms of source rocks with different types of organic matter. The organic matter of the Lucaogou Formation contains mostly two types of hydrocarbon generating macerals, the lamalginite and the telalginite based on physical and optical properties (texture, fluorescence, and optical reflectance). The lamalginite is a continuous sheet of less than 5 μm thick and greater than 50 μm in length. It has strong yellow fluorescence. The telalginite occurs as discontinuous short strips or pear-shaped objects with length of 10–30 μm and relatively weak fluorescence. The lamalginite-dominated shale has higher atomic H/C and lower atomic O/C ratios, indicating better hydrocarbon generation potential, whereas the telalginite-dominated shale has higher N and S heteroatom contents. The results of FT-IR spectroscopy of the kerogen indicate that the lamalginite-dominated shale is rich in aliphatic groups with long linear methylene sequences. The aromatic groups content is relatively low, but the carboxyl/carbon group (Cdouble bondO) content is high. The aliphatic group content of the telalginite-dominated shale is relatively low, with short-branched chains. The aromatic group content is relatively high. The methyl vibration signal directly connected to the benzene ring is strong, and the sulfoxide (Sdouble bondO) group has a high-intensity peak. Our results provide new insights into distinguishing organic matter types in the Lucaogou Formation and understanding the hydrocarbon generation mechanisms of source rocks in saline lake basins.

Evaluation of Source Rock Potential for Hydrocarbon Generation in Shallow Offshore, Lamu Basin, Kenya

The ever-increasing demand for oil and gas has driven its exploration in rather extreme conditions. In Lamu offshore, which is hitherto underexplored, most of the wells already drilled turned out dry save for a few wells with hydrocarbon shows despite the promising reservoir properties and related geological structures. This, therefore, necessitated a source rock evaluation study in the area to ascertain the presence and potential of the source rock by integrating the geochemical data analysis and petroleum system modeling. The shallow Lamu offshore source rock quantity, quality, and maturity have been estimated through the determination of the total organic carbon (TOC) average values, Kerogen typing, and Rock-Eval pyrolysis measurements respectively. Geochemical data for Kubwa-1, Mbawa-1, Pomboo-1, and Simba-1 were evaluated for determining the source rock potential for hydrocarbon generation. Petroleum system modeling was applied in evaluating geological conditions necessary for a successful charge within a software that integrated geochemical and petrophysical characterization of the sedimentary formations in conjunction with boundary conditions that include basal heat flow, sediment-water interface temperature, and Paleo-water depth. The average TOC of 0.89 wt % in the study area suggests a fair organic richness which seems higher in the late cretaceous (0.98 wt %) than in the Paleocene (0.81 wt %). Vitrinite reflectance and Tmax values in the study area indicate the possible presence of both mature and immature source rocks. Type III Kerogen was the most dominant Kerogen type, and gas shows are the most frequent hydrocarbon encountered in the Lamu Basin with a few cases registering type II/III and type II. The charge properties (i.e. Temperature, transformation ratio, and Vitrinite reflectance) over geologic time at each of the wells have been estimated and their spatial variation mapped as seen from the burial history and depth curves overlaid with temperature, transformation ratio, and Vitrinite reflectance respectively. From the upper cretaceous maturity maps, the results seem to favor near coastal regions where average TOC is about 1.4 wt %, Vitrinite reflectance is more than 0.5%, transformation ratio is more than 10%, and temperatures range from 80°C to 160°C. The results postulate the absence of a definitive effective source rock with a likelihood of having cases of potential and possible source rocks. Moreover, greater uncertainty rests on the source rock’s presence and viability tending toward the deep offshore. Geochemical analysis and petroleum system modeling for hydrocarbon source rock evaluation improved the understanding of the occurrence of the possible and potential source rocks and processes necessary for hydrocarbon generation.

Biodegradation of occluded hydrocarbons and kerogen macromolecules of the Permian Lucaogou shales,Junggar Basin,NW China

Three kerogen samples(JJZG-1,JJZG-2 and JJZG-3)isolated from the Permian Lucaogou shales of varying biodegradation levels(BLs≈0,3 and 7,respectively)were subjected to sequential stepwise pyrolysis combined with on-line detection of gas chromatography-mass spectrometry(GC-MS).Occluded fractions(bitumenⅡ)released at low-temperature steps(≥410℃)show consistent biodegradative signatures with that reported for solvent-extracted fractions(bitumenⅠ)of the original shales,e.g.,broad range of abundant n-alkanes,isoprenoids and regular hopanes for the non-biodegraded JJZG-1;trace n-alkanes and abundant hopanes for the moderately biodegraded JJZG-2;and no n-alkanes but still prominent hopanes including the microbially produced 25-nohopanes for the severely biodegraded JJZG-3.This consistency between bitumenⅡand bitumenⅠfractions indicates the biodegradability of the kerogenoccluded bitumenⅡwith limited protection from host kerogen.A minor level of protection was suggested by the trace distribution of n-alkanes in the bitumenⅡof JJZG-2,whereas the bitumenⅠhad no nalkanes.The kerogen itself was more resistant to biodegradation as reflected by the persistence of high abundances of both n-alkanes and hopanes in the high temperature(≥460℃)products of all three kerogen samples.However,the relative abundances of these product groups did show some evidence of biodegradation alteration,e.g.,ratios of n-C_(15)alkene/C_(27)hop-17(21)-ene at 510℃pyrolysis decreased by order of magnitude from the non-biodegraded(JJZG-1=27.4)to highly biodegraded(0.3 for JJZG-3)samples.The reduced biodegradation impact on the kerogen fraction(Cf.bitumen fractions)was also evident by the absence of 25-norhopanes in the high-temperature analysis of the JJZG-3 kerogen.

Assessment of hydrocarbon generation potential and thermal maturity of the deep offshore Lamu Basin, Kenya

In this study, the secondary well data for Cretaceous to Miocene cutting samples in four deep offshore exploration wells, i.e., Pomboo-1 in the north, Kubwa-1 in the central, Simba-1 and Kiboko-1 in the south of the deep offshore Lamu Basin were assessed for identifying source rock presence and examining thermal maturity of the source rocks. The 2D basin modelling was used to analyse the bulk gas transformation in the basin. Total organic carbon (TOC) content values for the wells range from 0.09 wt % to 2.23 wt % with an average of 0.78 wt %. The average organic richness is higher in the Upper Cretaceous (0.83 wt %) than in the Palaeogene (0.65 wt %), Lower Cretaceous (0.28 wt %) and Upper Jurassic (0.30 wt %). The S_(1) averages for the Upper Cretaceous are 3.76 mg HC/g rock in Pomboo-1 and 0.31mg HC/g rock in Kubwa-1. The S_(2) averages for the Upper Cretaceous are 5.00 mg HC/g rock in Pomboo-1 and 0.72 mg HC/g rock in Kubwa-1. Hydrogen index (HI) values vary between 4 and 512 mg HC/g TOC with an average of 157.09 mg HC/g TOC. Organic matters were identified as mixed types of Ⅱ-Ⅲ (oil and gas prone) and Ⅲ-Ⅳ (gas prone) kerogen in the potential source rocks. The HI and S_(2) yield values are exceptionally high for the observed TOC values in Pomboo-1. The vitrinite reflectance and Tmax values of deep offshore Lamu Basin are in the ranges of 0.38%–0.72% and 360–441 ℃, respectively. It suggests the existence of both immature and mature source rocks. Vitrinite reflectance maturity favours near coastal region in the Upper Cretaceous. These results explain why Pomboo-1, Kubwa-1, Simba-1 and Kiboko-1 wells were dry. The temperatures are still cool for hydrocarbon generation in deep offshore. The critical risk for deep offshore Lamu Basin is charge, primarily source presence, and a lack of definitive evidence of a deep-water marine source rock being present. The four wells penetrate good quality reservoir and seal rocks, but source rock presence and maturity remain the critical play risk in the deep offshore Lamu Basin.

Pore structure characterization and its effect on methane adsorption in shale kerogen

Pore structure characterization and its effect on methane adsorption on shale kerogen are crucial to understanding the fundamental mechanisms of gas storage,transport,and reserves evaluation.In this study,we use 3D scanning confocal microscopy,scanning electron microscopy(SEM),X-ray nano-computed tomography(nano-CT),and low-pressure N2 adsorption analysis to analyze the pore structures of the shale.Additionally,the adsorption behavior of methane on shales with different pore structures is investigated by molecular simulations.The results show that the SEM image of the shale sample obviously displays four different pore shapes,including slit pore,square pore,triangle pore,and circle pore.The average coordination number is 4.21 and the distribution of coordination numbers demonstrates that pores in the shale have high connectivity.Compared with the adsorption capacity of methane on triangle pores,the adsorption capacity on slit pore,square pore,and circle pore are reduced by 9.86%,8.55%,and 6.12%,respectively.With increasing pressure,these acute wedges fill in a manner different from the right or obtuse angles in the other pores.This study offers a quantitative understanding of the effect of pore structure on methane adsorption in the shale and provides better insight into the evaluation of gas storage in geologic shale reservoirs.

Mechanism of catalytic hydropyrolysis of sedimentary organic matter with MoS_2

MoS2 was used as an efficient catalyst for hydropyrolysis （Hypy） of three samples of sedimentary organic matter with different maturities. Through comparison with Soxhlet extraction （SE）, it was found that MoS2 catalytic Hypy can remarkably promote the yields of total chloroform extracts, saturates, aromatics, hopanes and steranes. In addition, the difference of biomarker parameters indicated that isomerization of covalently-bound biomarkers is much more difficult than their free counterparts. Meanwhile, the high conversion of total organic carbon （TOC） in MoS2 catalytic Hypy of organic matter proved that the presence of dispersed molybdenum sulfide accelerated the breaking of C-C bonds and the release of hydrocarbons. To address the catalytic mechanism, a series of control experiments based on free Hypy and catalytic Hypy were conducted. The results showed that the calculated atomic ratio of carbon conversion/hydrogen conversion for catalytic Hypy was much larger than the presumed value of 1/2, indicating that intensive hydrogenation took place and significantly influenced the distribution of liquid products. Analysis of stable hydrogen isotope data, infrared spectra and m/z 83 ion chromatograph of the saturate fraction further confirmed this hypothesis. The difference of S content changing （AS） between catalyst-free Hypy and catalytic Hypy, and the thermal characteristics of the catalyst, indicated that active H2S was definitely generated and it probably initiated free radical reactions in the early stage of hydropyrolysis of organic matter.

Analysis of imbibition of n-alkanes in kerogen slits by molecular dynamics simulation for characterization of shale oil rocks

Shale oil formations contain both inorganic and organic media.The organic matter holds both free oil in the pores and dissolved oil within the kerogen molecules.The free oil flow in organic pores and the dissolved oil diffusion in kerogen molecules are coupled together.The molecular flow of free n-alkanes is an important process of shale oil accumulation and production.To study the dynamics of imbibition process of n-alkane molecules into kerogen slits,molecular dynamics(MD)simulations are conducted.Effects of slit width,temperature,and n-alkane types on the penetration speed,dynamic contact angle,and molecular conformations were analyzed.Results showed that molecular transportation of n-alkanes is dominated by molecular structure and molecular motion at this scale.The space-confinement conformational changes of molecules slow down the filling speeds in the narrow slits.The n-alkane molecules with long carbon chains require more time to undergo conformational changes.The high content of short-chain alkanes and high temperature facilitate the flow of alkane mixtures in kerogen slits.Results obtained from this study are useful for understanding the underlying nanoscale flow mechanism in shale formations.

Molecular Structure of Kerogen in the Longmaxi Shale: Insights from Solid State NMR, FT-IR, XRD and HRTEM

Kerogen plays an important role in shale gas adsorption,desorption and diffusion.Therefore,it is necessary to characterize the molecular structure of kerogen.In this study,four kerogen samples were isolated from the organic-rich shale of the Longmaxi Formation.Raman spectroscopy was used to determine the maturity of these kerogen samples.Highresolution transmission electron microscopy(HRTEM),13 C nuclear magnetic resonance(13 C NMR),X-ray diffraction(XRD)and Fourier transform infrared(FT-IR)spectroscopy were conducted to characterize the molecular structure of the shale samples.The results demonstrate that VReqv of these kerogen samples vary from 2.3%to 2.8%,suggesting that all the kerogen samples are in the dry gas window.The macromolecular carbon skeleton of the Longmaxi Formation kerogen is mainly aromatic(fa’=0.56).In addition,the aromatic structural units are mainly composed of naphthalene(23%),anthracene(23%)and phenanthrene(29%).However,the aliphatic structure of the kerogen macromolecules is relatively low(fal*+falH=0.08),which is presumed to be distributed in the form of methyl and short aliphatic chains at the edge of the aromatic units.The oxygen-containing functional groups in the macromolecules are mainly present in the form of carbonyl groups(fac=0.23)and hydroxyl groups or ether groups(falO=0.13).The crystallite structural parameters of kerogen,including the stacking height(Lc=22.84?),average lateral size(La=29.29?)and interlayer spacing(d002=3.43?),are close to the aromatic structural parameters of anthracite or overmature kerogen.High-resolution transmission electron microscopy reveals that the aromatic structure is well oriented,and more than 65%of the diffractive aromatic layers are concentrated in the main direction.Due to the continuous deep burial,the longer aliphatic chains and oxygen-containing functional groups in the kerogen are substantially depleted.However,the ductility and stacking degree of the aromatic structure increases during thermal evolution.This study provides quantitative information on the molecular structure of kerogen samples based on multiple research methods,which may contribute to an improved understanding of the organic pores in black shale.

A rock physics model for the characterization of organic-rich shale from elastic properties

Kerogen content and kerogen porosity play a significant role in elastic properties of organic-rich shales. We construct a rock physics model for organic-rich shales to quantify the effect of kerogen content and kerogen porosity using the Kuster and Toks6z theory and the selfconsistent approximation method. Rock physics modeling results show that with the increase of kerogen content and kerogen-related porosity, the velocity and density of shales decrease, and the effect of kerogen porosity becomes more obvious only for higher kerogen content. We also find that the Poisson＇s ratio of the shale is not sensitive to kerogen porosity for the case of gas saturation. Finally, for the seismic reflection responses of an organic-rich shale layer, forward modeling results indicate the fifth type AVO re- sponses which correspond to a negative intercept and a positive gradient. The absolute values of intercept and gradient increase with kerogen content and kerogen porosity, and present predictable variations associated with velocities and density.

hale gas reservoir modeling and production evaluation considering complex gas transport mechanisms and dispersed distribution of kerogen

Stimulated shale reservoirs consist of kerogen,inorganic matter,secondary and hydraulic fractures.The dispersed distribution of kerogen within matrices and complex gas flow mechanisms make production evaluation challenging.Here we establish an analytical method that addresses kerogen-inorganic matter gas transfer,dispersed kerogen distribution,and complex gas flow mechanisms to facilitate evaluating gas production.The matrix element is defined as a kerogen core with an exterior inorganic sphere.Unlike most previous models,we merely use boundary conditions to describe kerogen-inorganic matter gas transfer without the instantaneous kerogen gas source term.It is closer to real inter-porosity flow conditions between kerogen and inorganic matter.Knudsen diffusion,surface diffusion,adsorption/desorption,and slip corrected flow are involved in matrix gas flow.Matrix-fracture coupling is realized by using a seven-region linear flow model.The model is verified against a published model and field data.Results reveal that inorganic matrices serve as a major gas source especially at early times.Kerogen provides limited contributions to production even under a pseudo-steady state.Kerogen properties’influence starts from the late matrix-fracture inter-porosity flow regime,while inorganic matter properties control almost all flow regimes except the early-mid time fracture linear flow regime.The contribution of different linear flow regions is also documented.