Impact of high water pressure on oil generation and maturation in Kimmeridge Clay and Monterey source rocks: Implications for petroleum retention and gas generation in shale gas systems

This study presents results for pyrolysis experiments conducted on immature Type II and IIs source rocks (Kimmeridge Clay, Dorset UK, and Monterey shale, California, USA respectively) to investigate the impact of high water pressure on source rock maturation and petroleum (oil and gas) generation. Using a 25 ml Hastalloy vessel, the source rocks were pyrolysed at low (180 and 245 bar) and high (500, 700 and 900 bar) water pressure hydrous conditions at 350 °C and 380 °C for between 6 and 24 h. For the Kimmeridge Clay (KCF) at 350 °C, Rock Eval HI of the pyrolysed rock residues were 30–44 mg/g higher between 6 h and 12 h at 900 bar than at 180 bar. Also at 350 °C for 24 h the gas, expelled oil, and vitrinite reflectance (VR) were all reduced by 46%, 61%, and 0.25% Ro respectively at 900 bar compared with 180 bar. At 380 °C the retardation effect of pressure on the KCF was less significant for gas generation. However, oil yield and VR were reduced by 47% and 0.3% Ro respectively, and Rock Eval HI was also higher by 28 mg/g at 900 bar compared with 245 bar at 12 h. The huge decrease in gas and oil yields and the VR observed with an increase in water pressure at 350 °C for 24 h and 380 °C for 12 h (maximum oil generation) were also observed for all other times and temperatures investigated for the KCF and the Monterey shale. This shows that high water pressure significantly retards petroleum generation and source rock maturation. The retardation of oil generation and expulsion resulted in significant amounts of bitumen and oil being retained in the rocks pyrolysed at high pressures, suggesting that pressure is a possible mechanism for retaining petroleum (bitumen and oil) in source rocks. This retention of petroleum within the rock provides a mechanism for oil-prone source rocks to become potential shale gas reservoirs. The implications from this study are that in geological basins, pressure, temperature and time will all exert significant control on the extent of petroleum generation and source rock maturation for Type II source rocks, and that the petroleum retained in the rocks at high pressures may explain in part why oil-prone source rocks contain the most prolific shale gas resources.     

Long‐term Holocene groundwater fluctuations in a chalk catchment: evidence from Rock‐Eval pyrolysis of riparian peats

The depositional history of peat‐dominated wetlands can be used to understand palaeoclimate and palaeohydrology and also constrain the impacts of future climate change. However, in chalkland valleys, seasonal water table fluctuations and a high alkalinity have diminished key environment indicators such as pollen, and there is a need for alternative investigative techniques. The method of Rock‐Eval pyrolysis can track changes in organic matter source and degradation, potentially relating to historic changes in vegetation cover. This is the first Rock‐Eval on cores from a groundwater‐dependent riparian chalk valley wetland combined with radiocarbon dating. The dating showed that the cores represented approximately 4000 years of depositional history. Changes in hydrocarbon chemistry including normal alkane composition of the peat indicated shifts of around 500 to 1000 years between terrestrial and more aquatic species, relating to periods of climate wetness. These climatic shifts are broadly consistent with other evidence from ombrotrophic peatland and lacustrine sediments across northwest Europe. However, the connection between climate wetness and groundwater dependent chalkland wetlands is complicated by external anthropogenically driven factors relating to land use and vegetation cover changes in the catchment. Nonetheless, this study suggests that Rock‐Eval pyrolysis is a useful and cost‐effective tool that can provide evidence for long‐term Holocene groundwater fluctuations. Copyright © 2016 British Geological Survey.     

Experimental investigation of thermal maturation on shale reservoir properties from hydrous pyrolysis of Chang 7 shale,Ordos Basin

Thermal maturity has a significant impact on hydrocarbon generation and the storage capacity within shales, but explicit and quantitative characterization of that impact on continental shales is scarce. To better understand how thermal maturation affects the organic and inorganic changes of the continental shale reservoirs, hydrous pyrolysis was performed to simulate the maturation process. TOC, Rock-Eval and adsorption isotherms tests were used to obtain various geochemical parameters of the shale solid residues. The results indicate that with pyrolysis temperature increasing from ambient temperature to 550 °C, the vitrinite reflectance increases from 0.5% to 2.5% Ro and the TOC (total organic carbon) loss weight reaches 25%. Regarding porosity, the fraction of micro-to meso-pores in the shale increases with an increase in the pyrolysis temperature, whereas the macro-pores do not change significantly. The total amount of gas adsorption does not necessarily increase as the TOC is consumed, but the gas adsorption capacity per unit of TOC increases with increasing thermal maturity. Our finding provides theoretical modelling for identifying shale gas development prospective zones according to thermal maturity mapping and for predicting quantitatively the geochemical and inorganic changes that occur with thermal evolution.     

Origins and maturity of organic matter in mid-Cretaceous black shales from ODP Site 1138 on the Kerguelen Plateau

We have conducted elemental, isotopic, and Rock-Eval analyses of Cenomanian–Santonian sediment samples from ODP Site 1138 in the southern Indian Ocean to assess the origin and thermal maturity of organic matter in mid-Cretaceous black shales found at this high-latitude location. Total organic carbon (TOC) concentrations range between 1 and 20 wt% in black to medium-gray sediments deposited around the Cenomanian–Turonian boundary. Results of Rock-Eval pyrolysis indicate that the organic matter is algal Type II material that has experienced modest alteration. Important contributions of nitrogen-fixing bacteria to the amplified production of organic matter implied by the high TOC concentrations is recorded in δ¹⁵N values between −5 and 1‰, and the existence of a near-surface intensified oxygen minimum zone that favored organic carbon preservation is implied by TOC/TN ratios between 20 and 40. In contrast to the marine nature of the organic matter in the Cenomanian–Turonian boundary section, deeper sediments at Site 1138 contain evidence of contributions land-derived organic matter that implies the former presence of forests on the Kerguelen Plateau until the earliest Cenomanian.     

Using Rock‐Eval 6 pyrolysis for tracking fossil organic carbon in modern environments: implications for the roles of erosion and weathering

This work relates to the debate on the fossil organic carbon (FOC) input in modern environments and its possible implication for the carbon cycle, and suggests the use of Rock‐Eval 6 pyrolysis as a relevant tool for tracking FOC in such environments. Considering that such a delivery is mainly due to supergene processes affecting the continental surface, we studied organic matter in different reservoirs such as bedrocks, alterites, soils and rivers in two experimental catchments at Draix (Alpes de Haute Provence, France). Samples were subjected to geochemical (Rock‐Eval 6 pyrolysis) investigations and artificial bacterial degradations. After comparing the geochemical fingerprint of samples, geochemical markers of FOC were defined and tracked in the different reservoirs. Our results confirm the contribution of FOC in modern soils and rivers and display the various influences of weathering and erosional processes on the fate of FOC during its exchange between these pools. In addition, the contrasting behaviour of these markers upon the supergene processes has also highlighted the refractory or labile characters of the fossil organic matter (FOM). Bedrock to river fluxes, controlled by gully erosion, are characterized by a qualitative and quantitative preservation of FOM. Bedrock to alterite fluxes, governed by chemical weathering, are characterized by FOC mineralization without qualitative changes in deeper alterites. Alterite to soils fluxes, controlled by (bio)chemical weathering, are characterized by strong FOC mineralization and qualitative changes of FOM. Thus weathering and erosional processes induce different FOM evolution and affect the fate of FOC towards the global carbon cycle. In this study, gully erosion would involve maintenance of an ancient sink for the global carbon cycle, while (bio)chemical processes provide a source of CO₂. Finally, this study suggests that Rock‐Eval 6 pyrolysis can be considered as a relevant tool for tracking FOC in modern environments. Copyright © 2006 John Wiley & Sons, Ltd.     

Effect of artificial maturation on carbazole distributions, as revealed by the hydrous pyrolysis of an organic-sulphur-rich source rock (Ghareb Formation, Jordan)

Hydrous pyrolysis experiments were performed on the Ghareb Formation (Upper Cretaceous, Jordan), a carbonate- and organic-rich (TOC 19.6%) source rock, using a temperature range of 200 to 360°C (72 h). The original sediment contains only low amounts of carbazoles, (maximum 2.2 μg/g bitumen for 1-methylcarbazole). With increasing thermal maturation, intense generation begins at temperatures only in excess of 300°C, reaching a maximum at 360°C. Likewise, during natural maturation, generation occurs at later stages of maturity (e.g. for Tithonian source rocks at >0.81% R_r and for Posidonia Shale at >0.88% R_r). Some isomeric changes during hydrous pyrolysis do not resemble those in nature whereas others do. The relative abundances of selected C₁- and C₂-alkylcarbazoles on ternary diagrams reveal differences, whereas the benzo[a]carbazole/benzo[a]carbazole+benzo[c]carbazole ratio is closely similar. The latter result supports the contention that maturation plays a key role in controlling carbazole distributions in source rocks. However, the results for alkylcarbazoles, especially the C₂-carbazoles, are not easy to interpret.     

Release of sulfur- and oxygen-bound components from a sulfur-rich kerogen during simulated maturation by hydrous pyrolysis

An immature sulfur-rich marl from the Gessosso-solfifera Formation of the Vena del Gesso Basin (Messinian, Italy) has been subjected to hydrous pyrolysis (160 to 330°C) to simulate maturation under natural conditions. The kerogen of the unheated and heated samples was isolated and the hydrocarbons released by selective chemical degradation (Li/EtNH₂ and HI/LiAlH₄) were analysed to allow a study of the fate of sulfur- and oxygen-bound species with increasing temperature. The residues from the chemical treatments were also subjected to pyrolysis–GC to follow structural changes in the kerogens. In general, with increasing hydrous pyrolysis temperature, the amounts of sulfide- and ether-bound components in the kerogen decreased significantly. At the temperature at which the generation of expelled oil began (260°C), almost all of the bound components initially present in the unheated sample were released from the kerogen. Comparison with an earlier study of the extractable organic matter using a similar approach and the same samples provides molecular evidence that, with increasing maturation, solvent-soluble macromolecular material was initially released from the kerogen, notably as a result of thermal cleavage of weak carbon–heteroatom bonds (sulfide, ester, ether) even at temperatures as low as 220°C. This solvent-soluble macromolecular material then underwent thermal cleavage to generate hydrocarbons at higher temperatures. This early generation of bitumen may explain the presence of unusually high amounts of extractable organic matter of macromolecular nature in very immature S-rich sediments.     

Origin of low-molecular-weight alkylthiophenes in pyrolysates of sulphur-rich kerogens as revealed by micro-scale sealed vessel pyrolysis

Micro-scale sealed vessel (MSSV) pyrolysis experiments have been conducted at temperatures of 150, 200, 250, 300, 330 and 350°C for various times on a thermally immature Type II-S kerogen from the Maastrichtian Jurf ed Darawish Oil Shale (Jordan) in order to study the origin of low-molecular-weight (LMW) alkylthiophenes. These experiments indicated that the LMW alkylthiophenes usually encountered in the flash pyrolysates of sulphur-rich kerogens are also produced at much lower pyrolysis temperatures (i.e. as low as 150°C) as the major (apart from hydrogen sulfide) sulphur-containing pyrolysis products. MSSV pyrolysis of a long-chain alkylthiophene and an alkylbenzene indicated that at 300°C for 72 h no β-cleavage leading to generation of LMW alkylated thiophenes and benzene occurs. In combination with the substantial production of LMW alkylthiophenes with a linear carbon skeleton at these conditions, this indicated that these thiophenes are predominantly formed by thermal degradation of multiple (poly)sulfide-bound linear C₅–C₇ skeletons, which probably mainly originate from sulphurisation of carbohydrates during early diagenesis. LMW alkylthiophenes with linear carbon skeletons seem to be unstable at MSSV pyrolysis temperatures of ≥330°C either due to thermal degradation or to methyl transfer reactions. LMW alkylthiophenes with a branched carbon skeleton most likely derive from both multiple (poly)sulfide-bound branched C₅–C₇ skeletons and alkylthiophene units present in the kerogen.     

高温超高压模拟实验研究Ⅰ.温压条件对有机质成熟作用的影响

对不成熟泥炭样品进行了高压（0.1～2GPa）、高温（200℃～400℃）模拟实验,并对实验后样品的成熟度指标--镜质体反射率（Ro）进行了测定。结果显示,同一压力条件下,温度与镜质体反射率呈正相关;相同温度条件下,样品Ro值与压力呈负相关,说明压力同温度一样,是影响有机质成熟作用的一个重要因素,其存在会抑制有机质向高成熟演化。压力的这种作用有其内在的化学动力学机理。实验结果及实际地质现象都说明,压力作用在有机质演化过程中不可忽视。用模拟实验手段探讨压力的作用和影响,具有重要的理论及实际意义。     

煤成烃生成及排驱加水热模拟实验

用加水热模拟实验对采于我国胜利油田附近的石炭系太原组亮褐煤（R0＝0．56%）生烃潜力进行研究。煤样富含镜质组（74．5%）,壳质组少（8．8%）,惰性组占16．7%,其中镜质组以富氢的基质镜质体为主。煤样裂隙发育,形成于滨海沼泽相沉积环境。实验设200℃、230℃、260℃、290℃、320℃和350℃六个温度点,每个温度点加热72小时。实验结果表明该煤具有较高的生烃潜力和排油效率。其液态烃大量生成和排出始于R0＝0．76%（290℃）,在R0＝1．18%（320℃）时达高峰。气态产物从R0＝1．18%大量形成,直到R0＝1．53%（350℃）继续增大。实验分析认为煤的生烃能力除了与其有机质类型、有机质丰度等有关外,还与其形成的沉积环境有关,缺氧的还原环境是煤作为烃源岩形成和保存的有利沉积环境。裂隙的发育有助于煤成油的排驱和运移。