Effect of thermal maturation and organic matter content on oil shale fracturing

The Pabdeh Formation represents organic matter enrichment in some oil fields,which can be considered a source rock.This study is based on the Rock–Eval,Iatroscan,and electron microscopy imaging results before and after heating the samples.We discovered this immature shale that undergoes burial and diagenesis,in which organic matter is converted into hydro-carbons.Primary migration is the process that transports hydrocarbons in the source rock.We investigated this phenomenon by developing a model that simulates hydrocarbon generation and fluid pressure during kerogen-to-hydrocarbon conversion.Microfractures initially formed at the tip/edge of kerogen and were filled with hydrocarbons,but as catagenesis progressed,the pressure caused by the volume increase of kerogen decreased due to hydrocarbon release.The transformation of solid kerogen into low-density bitumen/oil increased the pressure,leading to the development of damage zones in the source rock.The Pabdeh Formation’s small porethroats hindered effective expulsion,causing an increase in pore fluid pressure inside the initial microfractures.The stress accumulated due to hydrocarbon production,reaching the rock’s fracture strength,further contributed to damage zone development.During the expansion process,microfractures preferentially grew in low-strength pathways such as lithology changes,laminae boundaries,and pre-existing microfractures.When the porous pressure created by each kerogen overlapped,individual microfractures interconnected,forming a network of microfractures within the source rock.This research sheds light on the complex interplay between temperature,hydrocarbon generation,and the development of expulsion fractures in the Pabdeh Formation,providing valuable insights for understanding and optimizing hydrocarbon extraction in similar geological settings.

Evolution of pore systems in low-maturity oil shales during thermal upgrading--Quantified by dynamic SEM and machine learning

In-situ upgrading by heating is feasible for low-maturity shale oil,where the pore space dynamically evolves.We characterize this response for a heated substrate concurrently imaged by SEM.We systematically follow the evolution of pore quantity,size(length,width and cross-sectional area),orientation,shape(aspect ratio,roundness and solidity)and their anisotropy—interpreted by machine learning.Results indicate that heating generates new pores in both organic matter and inorganic minerals.However,the newly formed pores are smaller than the original pores and thus reduce average lengths and widths of the bedding-parallel pore system.Conversely,the average pore lengths and widths are increased in the bedding-perpendicular direction.Besides,heating increases the cross-sectional area of pores in low-maturity oil shales,where this growth tendency fluctuates at<300℃ but becomes steady at>300℃.In addition,the orientation and shape of the newly-formed heating-induced pores follow the habit of the original pores and follow the initial probability distributions of pore orientation and shape.Herein,limited anisotropy is detected in pore direction and shape,indicating similar modes of evolution both bedding-parallel and bedding-normal.We propose a straightforward but robust model to describe evolution of pore system in low-maturity oil shales during heating.

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.

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.

Mechanism and reservoir simulation study of the autothermic pyrolysis in-situ conversion process for oil shale recovery

The autothermic pyrolysis in-situ conversion process (ATS) consumes latent heat of residual organic matter after kerogen pyrolysis by oxidation reaction, and it has the advantages of low development cost and exploitation of deep oil shale resources. However, the heating mechanism and the characteristic of different reaction zones are still unclear. In this study, an ATS numerical simulation model was proposed for the development of oil shale, which considers the pyrolysis of kerogen, high-temperature oxidation, and low-temperature oxidation. Based on the above model, the mechanism of the ATS was analyzed and the effects of preheating temperature, O_(2) content, and injection rate on recovery factor and energy efficiency were studied. The results showed that the ATS in the formation can be divided into five characteristic zones by evolution of the oil and O_(2) distribution, and the solid organic matter, including residue zone, autothermic zone, pyrolysis zone, preheating zone, and original zone. Energy efficiency was much higher for the ATS than for the high-temperature nitrogen injection in-situ conversion process (HNICP). There is a threshold value of the preheating temperature, the oil content, and the injection rate during the ATS, which is 400 °C, 0.18, and 1100 m3/day, respectively, in this study.

Investigation of Organic Matter Extraction from Moroccan Oil Shale

This study focuses on investigating the effect of various solvents on the supercritical extraction of organic matter from Moroccan oil shales, with the goal of determining the optimal operating conditions that result in a high yield of high-quality oil rich in aromatic compounds. The results of this study demonstrate that the extraction yield and quality of the extracted oil heavily depend on the chosen operating conditions for supercritical or subcritical extraction of organic matter from oil shale. Additionally, the study found that phenol can effectively degrade oil shale and enable extraction of nearly all the organic matter, even under mild conditions (T = 390˚C, P = 1.2 MPa, Time = 2.5 h. Furthermore, the oils obtained through this extraction process are of high quality, with a rich content of maltenes, and a higher concentration of aromatic compounds and lower levels of sulfur than those obtained using other solvents.

Investigation of Organic Matter Extraction from Moroccan Oil Shale

This study focuses on investigating the effect of various solvents on the supercritical extraction of organic matter from Moroccan oil shales, with the goal of determining the optimal operating conditions that result in a high yield of high-quality oil rich in aromatic compounds. The results of this study demonstrate that the extraction yield and quality of the extracted oil heavily depend on the chosen operating conditions for supercritical or subcritical extraction of organic matter from oil shale. Additionally, the study found that phenol can effectively degrade oil shale and enable extraction of nearly all the organic matter, even under mild conditions (T = 390˚C, P = 1.2 MPa, Time = 2.5 h. Furthermore, the oils obtained through this extraction process are of high quality, with a rich content of maltenes, and a higher concentration of aromatic compounds and lower levels of sulfur than those obtained using other solvents.

Laboratory study of the factors affecting hydraulic fracturing effect for inter-salt oil shale layers,Qianjiang Depression,China

This study aims to investigate the potential factors affecting hydraulic fracturing of inter-salt oil shale reservoirs in the Qianjiang Depression,China.Using the inter-salt shale samples,the re-crystallization seepage tests,rock mechanical tests under high temperature and pressure,salt rock creep tests,and direct shear tests were conducted.The testing results suggest several major factors that affect hydraulic fracturing effects in the end.First,the seepage of reservoir and fracturing fluid through hydraulic frac-tures leads to salt dissolution and crystallization,reducing the effective seepage area of fractures.Second,the salt crystal may block the pore throats or micro fractures after brine invades the shale,decreasing the overall permeability.Third,the low strength and obvious plasticity of inter-salt shale and the strong creep characteristics of salt rock raise difficulties for proppant to effectively support fracture walls,thereby sharply narrowing the hydraulic fracture width.Lastly,the weak interfaces(bedding planes and lithology interfaces)in inter-salt oil shale reservoirs restrict the height of hydraulic fractures,resulting in the disconnection of seepage channels between multiple inter-salt shale reservoirs.Thus,several factors together reduce reservoir permeability,weaken the fluid flow capacity in the fracture,narrow the fracture width,and limit the effective stimulation volume,resulting in weaken the effect hydraulic fracturing.

Organic Geochemistry of the Early Jurassic Oil Shale from the Shuanghu Area in Northern Tibet and the Early Toarcian Oceanic Anoxic Event

This paper presents new geological and geochemical data from the Shuanghu area in northern Tibet, which recorded the Early Toarcian Oceanic Anoxic Event. The stratigraphic succession in the Shuanghu area consists mostly of grey to dark-colored alternating oil shales, marls and mudstones. Ammonite beds are found at the top of the Shuanghu oil shale section, which are principally of early Toarcian age, roughly within the Harplocearas falciferrum Zone. Therefore, the oil shale strata at Shuanghu can be correlated with early Toarcian black shales distributing extensively in the European epicontinental seas that contain the records of an Oceanic Anoxic Event. Sedimentary organic matter of laminated shale anomalously rich in organic carbon across the Shuanghu area is characterized by high organic carbon contents, ranging from 1.8% to 26.1%. The carbon isotope curve displays the δ 13C values of the kerogen (δ 13Ckerogen) fluctuating from –26.22 to –23.53‰ PDB with a positive excursion close to 2.17‰, which, albeit significantly smaller, may also have been associated with other Early Toarcian Oceanic Anoxic Events (OAEs) in Europe. The organic atomic C/N ratios range between 6 and 43, and the curve of C/N ratios is consistent with that of the δ 13Ckerogen values. The biological assemblage, characterized by scarcity of benthic organisms and bloom of calcareous nannofossils (coccoliths), reveals high biological productivity in the surface water and an unfavorable environment for the benthic fauna in the bottom water during the Oceanic Anoxic Event. On the basis of organic geochemistry and characteristics of the biological assemblage, this study suggests that the carbon-isotope excursion is caused by the changes of sea level and productivity, and that the black shale deposition, especially oil shales, is related to the bloom and high productivity of coccoliths.

Pyrolysis characteristics of a North Korean oil shale

Pyrolysis characteristics of a North Korean oil shale and its pyrolysates were investigated in this paper. The pyrolysis experiments were conducted below 600 ℃ at a heating rate of 10, 15, 20 and 25 ℃/min, respectively. The kinetics data were calculated using both integral and differential methods with the assumption of first order kinetics. The results show that the averaged oil content of the North Korean oil shale is about 12.1 wt% and its heat value is 13,400 kJ/kg. The oil yields at different retorting temperatures show that the higher the retorting temperature the greater the oil and retorting gas yields. The optimal retorting temperature for the North Korean oil shale is about 500 ℃. The properties of the North Korean shale oil including density, viscosity, flash point and freezing point are found to be relatively low compared with those of shale oil from FuShun, China. The gasoline fraction, diesel fraction and heavy oil fraction account for 11.5 wt%, 41.5 wt% and 47 wt%, respectively. The major pyrolysis gases are ca4 （the most abundant）, H2, CO2, H2S, CO, and C2-C5 hydrocarbons. The heat value of retorting gas is more than 900 kJ/mol, and the retorting gas has high sulfur content.

Removal of Cu2＋ from Aqueous Solutions Using Na-A Zeolite from Oil Shale Ash

Na-A zeolite was synthesized using oil shale ash （OSA）, which is a solid by-product of oil shale proc- essing. The samples were characterized by various techniques, such as scanning electron microscopy, X-ray diffrac- tion and Brunaner Emmet Teller method. The batch isothermal equilibrium adsorption experiments were performed to evaluate the ability of Na-A zeolite for removal of Cu （II） from aqueous solutions. The effects of operating pa- rameters, such as concentration of copper solutions, adsorbent dosages, pH value of solutions and temperature, on the adsorption efficiency were investigated. The equilibrium adsorption data were fitted with Langmuir and Freundlich models. The maximum adsorption capacity of Na-A zeolite obtained from the Langmuir adsorption iso- therm is 156.7 mg.g-t of Cu （lI）. The increase of pH level in the adsorption process suggests that the uptake of heavy metals on the zeolite follows an ion exchange mechanism. The batch kinetic data fit the pseudo-second order equation well. The thermodynamic parameters, such as changes in Gibbs free energy （AG）, enthalpy （AH） and en- tropy （AS）, are used to predict the nature of the adsorption process. The negative AG values at different tempera- tures confirm that the adsorption processes are spontaneous.

Chemo-and Biostratigraphy of the Jurassic Oil Shales from the Qiangtang Basin,Northern Tibet,China:A Case Study of the Toarcian Oceanic Anoxic Event

The marine oil shales of the Qiangtang Basin, northern Tibet, exposed in the Biluo Co, Tuonamu, Shenglihe and Changsheshan areas are believed to be important petroleum source rocks. This work comprehensively analyzed the carbon isotopes, trace elements, and calcareous nannofosills, ammonites and bivalves of the Biluo Co section in the Qiangtang Basin. The organic carbon isotopes show a positive excursion close to 2.17‰（relative to PDB）, which, albeit significantly smaller, may also be associated with other Early Toarcian Oceanic Anoxic Events（T-OAE） in the European epicontinental seas and the Tethyan continental margins. Coinciding with the Early Toarcian transgression, the oxygen deficiency in bottom water had led to dysoxic-anoxic conditions and deposition of black shales lacking benthic fauna. Under such condition, the redox-sensitive trace metals such as Mo, V, Ni, Cr, and U were enriched, in conjunction with high planktonic productivity of Watznaueriaceae calcareous nannofossils. Comparison of the results with the records of chemo-and biostratigraphy, as well as the palaeogeography during the Early Jurassic suggests that the anoxia linked to the Early Toarcian oceanic anoxic event was mainly caused by the high surface water temperature, sea-level rise and an increase of surface water productivity.

Elemental characteristics and paleoenvironment reconstruction： a case study of the Triassic lacustrine Zhangjiatan oil shale, southern Ordos Basin, China

Using trace elements to reconstruct paleoenvironment is a current hot topic in geochemistry. Through analytical tests of oil yield, ash yield, calorific value, total sulfur, major elements, trace elements, and X-ray diffraction, the quality, mineral content, occurrence mode of elements, and paleoenvironment of the Zhangjiatan oil shale of the Triassic Yanchang Formation in the southern Ordos Basin were studied. The analyses revealed relatively high oil yield(average 6.63%) and medium quality. The mineral content in the oil shale was mainly clay minerals,quartz, feldspar, and pyrite; an illite–smectite mixed layer comprised the major proportion of clay minerals. Compared with marine oil shale in China, the Zhangjiatan oil shale had higher contents of quartz, feldspar, and clay minerals, and lower calcite content. Silica was mainly in quartz and Fe was associated with organic matter, which is different from marine oil shale. The form of calcium varied. Cluster analyses indicated that Fe, Cu, U, V, Zn, As,Cs, Cd, Mo, Ga, Pb, Co, Ni, Cr, Sc, P, and Mn are associated with organic matter while Ca, Na, Sr, Ba, Si, Zr, K,Al, B, Mg, and Ti are mostly terrigenous. Sr/Cu, Ba/Al, V/(V+ Ni), U/Th, AU, and δU of oil shale samples suggest the paleoclimate was warm and humid, paleoproductivity of the lake was relatively high during deposition of the shale—which mainly occurred in fresh water—and the paleo-redox condition was dominated by reducing conditions. Fe/Ti ratios of the oil shale samples suggest clear hydrothermal influence in the eastern portion of the study area and less conspicuous hydrothermal influence in the western portion.

Combustion characteristics of Daqing oil shale and oil shale semi-cokes

Thermo-gravimetric-analysis(TGA) was used to analyze the combustion characteristics of an oil shale and semi-cokes prepared from it.The effect of prior pyrolysis and TGA heating rate on the combustion process was studied.Prior pyrolysis affects the initial temperature of mass loss and the ignition temperature.The ignition temperature increases as the volatile content of the sample decreases.TG/DTG curves obtained at different heating rates show that heating rate has little effect on ignition temperature.But the peak of combustion shifts to higher temperatures as the heating rate is increased.The Coats-Redfern integration method was employed to find the combustion-reaction kinetic parameters for the burning of oil shale and oil shale semi-coke.

Depositional conditions and modeling of Triassic Oil shale in southern Ordos Basin using geochemical records

Based on the element geochemistry and biomarkers of the oil shale from the Chang 7 sub-unit in the southern Ordos Basin,the depositional conditions and organic source of the oil shale are discussed.Biomarkers analyses show that the oil shale has a homologous organic matter source,with a mix of plankton and advanced plants.U/Th and V/Ni ratios suggest that the redox condition is dominated by a reducing condition,and the degree of anoxia in the Tongchuan area is higher than that of the Xunyi area.Sr/Ba ratios illustrate that the oil shale is deposited in fresh water and the paleosalinity in the Tongchuan area is slightly higher.Fe/Ti ratios imply that the Tongchuan area underwent obvious hydrothermal fluid activities.Sr/Cu ratios show warm and humid paleoclimate in both areas.As assessed by(La/Yb)NASC,the deposition rate in the Tongchuan area is relatively lower.Fe/Co and Th/U ratios suggest that the paleo-water-depth in the Tongchuan area is deeper.The source rock could have the advance plants source,which must have close relationship with the Qinling orogeny.Comparing the paleoenvironment,the Tongchuan area has better depositional conditions,and is the key oil shale exploration area in the southern Ordos Basin.

Reaction mechanism and kinetics of pressurized pyrolysis of Chinese oil shale in the presence of water

A study of reaction mechanisms and chemical kinetics of pressurized pyrolysis of Chinese Liushuhe oil shale in the presence of water were conducted using an autoclave for simulating and modeling in-situ underground thermal degradation.It was found that the oil shale was first pyrolyzed to form pyrobitumen,shale oil,shale gas and residue,then the pyrobitumen was further pyrolyzed to form more shale oil,shale gas,and residue.It means that there are two consecutive and parallel reactions.With increasing temperature,the pyrobitumen yield,as intermediate,first reached a maximum,then decreased to approximately zero.The kinetics results show that both these reactions are first order.The activation energy of pyrobitumen formation from oil shale is lower than that of shale oil formation from pyrobitumen.

Insight into the structural features of organic species in Fushun oil shale via thermal dissolution

Fushun oil shale(FOS) was subjected to thermal dissolution(TD) under different conditions. The results show that the optimal solvent, temperature, time, and ratio of solvent to FOS are ethanol, 300 °C, 2 h, and 5 ml·g^(-1),respectively and the corresponding yield of the soluble portion(SP) is 32.2%(daf), which is much higher than the oil content of FOS(ca. 6%), suggesting that TD in ethanol is an excellent way to extract organics from FOS.According to 3 direct analyses, aliphatic moieties in FOS are the most abundant followed by C\\O-containing moieties and each cluster in FOS has 3 conjugated aromatic rings on average with fewer substituents. According to the analysis with a gas chromatograph/mass spectrometer, alkanes are predominant in all the SPs. A number of alkenes were identified in the SPs from the TD, while none of the alkenes were detected in acetone-SP obtained at room temperature, implying that the TD can destroy the π-π and intertwining interactions between alkenes and macromolecular structures in FOS. Moreover, a small amount of alkyl-substituted phenols and alkoxysubstituted phenols were detected in ethanol-SP from the TD, which could be the products from ethanolyzing the macromolecular moiety of FOS.

An advanced ash fusion study on the melting behaviour of coal,oil shale and blends under gasification conditions using picture analysis and graphing method

This study investigates the potential of solid fuel blending as an effective approach to manipulate ash melting behaviour to alleviate ashrelated problems during gasification,thus improving design,operability and safety.The ash fusion characteristics of Qinghai bituminous coal together with Fushun,Xinghua and Laoheishan oil shales(and their respective blends)were quantified using a novel picture analysis and graphing method,which incorporates conventional ash fusion study,dilatometry and sintering strength test,in a CO/CO_(2)atmosphere.This imagebased characterisation method was used to monitor and quantify the complete melting behaviour of ash samples from room temperature to 1520℃.The impacts of blending on compositional changes during heating were determined experimentally via Xray diffraction and validated computationally using FactSage.Results showed that the melting point of Qinghai coal ash to be the lowest at 1116℃,but would increase up to 1208℃,1161℃and 1160℃with the addition of 30%50%of Laoheishan,Fushun,and Xinghua oil shales,respectively.The formation of highmelting anorthite and mullite structures inhibits the formation of lowmelting hercynite.However,the sintering point of Qinghai coal ash was seen to decrease from 1005℃to 855℃,834℃,and 819℃in the same blends due to the formation of lowmelting aluminosilicate.Results also showed that blending directly influences the sintering strength during the various stages of melting.The key finding from this study is that it is possible to mitigate against the severe ash slagging and fouling issue arising from high calcium and iron coals by cogasification with a high silicaalumina oil shale.Moreover,blending coals with oil shales can also modify the ash melting behaviour of fuels to create the optimal ash chemistry that meets the design specification of the gasifier,without adversely affecting thermal performance.

Elemental characteristics of lacustrine oil shale and its controlling factors of palaeo-sedimentary environment on oil yield： a case from Chang 7 oil layer of Triassic Yanchang Formation in southern Ordos Basin

As an important unconventional resource, oil shale has received widespread attention. The oil shale of the Chang 7 oil layer from Triassic Yanchang Formation in Ordos Basin represents the typical lacustrine oil shale in China. Based on analyzing trace elements and oil yield from boreholes samples, characteristics and paleo-sedi- mentary environments of oil shale and relationship between paleo-sedimentary environment and oil yield were studied. With favorable quality, oil yield of oil shale varies from 1.4% to 9.1%. Geochemical data indicate that the paleo-redox condition of oil shale＇s reducing condition from analyses of V/Cr, V/（V ＋ Ni）, U/Th, δU, and authi genic uranium. Equivalent Boron, Sp, and Sr/Ba illustrate that paleosalinity of oil shale is dominated by fresh water. The paleoclimate of oil shale is warm and humid by calculating the chemical index of alteration and Sr/Cu. Fe/Ti and （Fe ＋ Mn）/Ti all explain that there were hot water activities during the sedimentary period of oil shale. In terms of Zr/Rb, paleohydrodynamics of oil shale is weak. By means of Co abundance and U/Th, paleo-water-depth of oil shale is from 17.30 to 157.26 m, reflecting sedimentary environment which is mainly in semi deep-deep lake facies. Correlation analyses between oil yield and six paleoenvironmental factors show that the oil yield of oil shale is mainly controlled by paleo-redox conditions, paleoclimate, hot water activities, and depth of water.Paleosalinity and paleohydrodynamics have an inconspicuous influence on oil yield.

Oil shale resources in China and their utilization

The unconventional oil and gas resources presented in oil shales have meant these potential sources of hydrocarbons, which has become a research focus. China contains abundant oil shale resources, ranking fourth in the world, with ca. 7 254.48 x 108 t within 24 provinces, including 48 basins and 81 oil shale deposits. A- bout 48% of the total oil shale resources are concentrated in the eastern resource region, with a further 22% in the central resource region. 65 % of the total quantity of oil shale resources is present at depths of 0-500 m, with 17% of the total resources being defined as high-quality oil shales yielding more than 10% oil by weight. Chinese oil shale resources are generally hosted by Mesozoic sediments that account for 78% of the total re- sources. In terms of the geographical distribution of these resources, some 45% are located in plain regions, and different oil shale basins have various characteristics. The oil shale resources in China represent a highly prospective future source of hydrocarbons. These resources having potential use not only in power generation and oil refining but also in agriculture, metal and chemical productions, and environmental protection.