A Study on Hydrocarbon—Generating Potential and Kinetics of Source—Rock Pyrolysis

A study on the potential and kinetics of hydrocarborn(HC) generation of 30 source-rock samples from a certain depression has been made by means of ROCK-EVAL technique .In the pyrolysis experiment, the source material types, maturation and hydrocarbon-generating potential of source rocks from three Upper Jurassic horizons of that area have been evaluated in terms of such indicators as the type-index, hydrocarbon-generating potential and maximum pyrolysis temperaturw(Tmax) .The results show that the pyrolysis HC yield of immature source rocks is much higher than that of mature rocks in case that the source mateuial is of high quantity and organic matter is abundant, which suggests that it is important for evaluating the HC-generating potential to use immature samples for pyrolysis.In the pyrolytic simulation experiments on other two immature samples,it was found that the hydrocarbon yield is temperature-dependent, and thereafter the kinetical parameters for source rocks, such as reactional grade, appearant activation energy and frequency factor were calculated.     

Liquid hydrocarbon source-rock potential of mid-Cretaceous coals and coal measures in the Middle Benue Trough of Nigeria

Received: 23 March 1999 / Accepted: 25 August 1999     

包气带对三氯乙烯的吸附行为研究

有机污染物在包气带的吸附行为,直接影响有机污染物在环境中的迁移、转化等过程。采用浅层和深层包气带样品,利用批实验的方法研究不同有机碳含量的样品对三氯乙烯(TCE)的吸附行为。研究表明,包气带表层土壤比深层土壤的有机碳含量高,可能存在竞争吸附的问题,说明该土壤的吸附行为是以矿物吸附为主、有机质吸附为辅的类型;表层土壤的吸附具有较好的线性行为,不存在饱和吸附量;深层土壤有机碳含量低,其吸附为非线性的。     

Production, preservation and prediction of source-rock facies in deltaic settings

This article hypothesizes that production and preservation of source-rock type facies in deltaic systems, both landward and seaward of a coastline, is mutually exclusive, time-successive and related to the dynamics of relative sea level. Sedimentologic research in the Holocene Mississippi and Rhône delta complexes suggests that rheotrophic peats and associated organic-rich beds preferably accumulate in the accommodation space created behind landward stepping shorelines in a transgressive systems tract (TST). Such a setting also allows for a sufficient supply of recharging fresh nutrient-rich groundwater into the peat forming mires [Kosters, E.C., Suter, J.R., 1993. Facies relationships and systems tracts in the late Holocene Mississippi Delta Plain. Journal of Sedimentary Petrology 63 (4) 727–733.]. Independently carried-out quantitative paleoecological studies in the same delta systems (and in addition in the Orinoco and Po deltas) suggest that in a progradational setting (highstand systems tract/HST), seasonally discharged nutrient- and sediment-laden river waters on the shelf may give rise to anoxia or dysoxia. Subsequent overfertilization of the shelf leads to accumulation of organic-rich mud belts on the shelf [VanderZwaan, G.J., Jorissen, F.J., 1991. Biofacial patterns in river-induced anoxia. In: Tyson, R.V., Pearson, T.H. (Eds.), Modern and Ancient Continental Shelf Anoxia. Geological Society of London, Special Publication no. 58, pp. 65–82.]. Thus, production and preservation of source-rock type facies landward of a shoreline (as peats and related sediments) is preferred in a TST, when accommodation space and nutrient supply are landward of the shoreline. Vice versa, production and preservation of such facies seaward of a shoreline (as organic-rich shelf muds) occurs preferentially in a highstand systems tract. In that situation, accommodation space is on the shelf, where river-fed nutrients are supplied as well. This hypothesis suggests further potential for application of sequence stratigraphic concepts for improved understanding of the occurrence of source-rock type facies.     

Artificial bacterial degradation and hydrous pyrolysis of suberin: Implications for hydrocarbon generation of suberinite

The organic maceral suberinite is widely believed to be a contributor to immature or low mature oils with R_o < 0.5% in some coal and terrigenous sequences. However, its evolution of hydrocarbon generation, especially in the relatively high maturation stage of R_o > 0.5%, has not been sufficiently characterized. This issue was addressed herein using periderm cork tissues of the modern angiosperm Quercus suber (suberin), which is a possible bio-precursor of suberinite, in artificial bacterial degradation and hydrous pyrolysis experiments. Integrated studies were conducted, including analyses on the compositions of hydrocarbon yields and the content variations that were generated during the experiments, gas chromatography (GC) analyses of generated oils and spectral fluorescence observations, and Rock-Eval and Fourier Transform Infrared (FTIR) microspectroscopic studies on solid residues. Analytical results indicate that suberin and suberinite have long and complex hydrocarbon generation histories. In general, the hydrocarbon that is generated during bacterial degradation is predominantly gas and present in relatively limited amounts, while the oils mainly are generated during hydrous pyrolysis. Furthermore, the oil generation has two peaks that correspond to R_o of approximately 0.35–0.50% and 0.80–1.10%. In composition, the early generated oil mainly consists of long chain waxy and oxygen containing compounds, while the late generated oil is relatively enriched in aromatic compounds. These features can be ascribed to the chemical nature (e.g., composition and structure) of suberin. It is a type of insoluble and high molecular weight polyester compound that contains large quantities of long chain structure dicarboxylic acids and alcohols. Consequently, the deoxygenization of these compounds can take place under relatively low thermodynamic conditions, generating liquid oil that is dominated by a long chain structure and oxygen-containing waxy compounds. In contrast, the degradation of the phenolic compounds results in the second oil generation peak. Therefore, suberinite has a two stage and relatively long oil generation history and is a good bio-precursor for coal-derived oil generation.     

土壤中有机碳含量对三氯乙烯的吸附影响实验

采用某地区土壤样品,利用批实验的方法,研究不同有机碳含量的土壤样品对三氯乙烯(TCE) 的吸附行为.研究表明,土壤样品中,由于有机碳含量不同,有机污染物三氯乙烯(TEC)的吸附量不同,存在有机碳含量的阈值区间(foc*).最小foc*=0.702%,最大foc*=1.831%,当foc<0.702%时,TCE吸附量随土壤样品的有机碳含量变化较小,基本不随foc变化而发生较大变化;在0.702%1.831%时,TCE吸附量随土壤样品的有机碳含量变化又变得平缓,基本上又不随foc升高而发生较大的变化.     

Relations between stream sediment and source-rock mineralogy,Piney Creek Basin,Wyoming

The areal distribution of stream sediment and source-rock heavy mineralogy was studied to determine the mineralogical relations between source and derived sediment in the Piney Creek drainage basin of Wyoming. Heavy-mineral distribution in the streams was characterized using factor analysis. The results of analyses show that for an actively degrading stream system, the heavy-mineral composition of stream sediment is controlled to a considerable extent by the composition of local sediment sources and by continuous addition of detritus from bank cutting. Only the most common minerals from upstream sources persist as statistically significant variables downstream. In some cases the heavy-mineral mineral composition of stream sediment can be controlled by comparatively few, or volumetrically rare source rocks, even though more abundant source rocks supply a wide range of heavy minerals. Specific drainage configurations such as lakes and proximity of streams to major sediment sources significantly modify sediment mineralogy immediately downstream.     

邻菲罗啉对蒙脱石吸附性的影响

为了提高蒙脱石对大分子物质的吸附性,利用邻菲罗啉可与过渡金属离子形成配合物的性质,用两种方法对蒙脱石加以改性。通过测定改性蒙脱石对染料的脱色性及分析XRD图,研究邻菲罗啉的配合物的生成方式对蒙脱石层间结构及吸附性能的影响,并探讨了改性蒙脱石的热稳定性。结果表明,邻菲罗啉能够进一步撑开层间含有过渡金属离子的蒙脱石片层,使层间距明显增大到1.76nm以上;采用过渡金属离子为先驱体,先插入蒙脱石层间、再原位生成配合物的两步法能获得既增大层间距、又提高有序度的良好效果;改性蒙脱石在400℃以下具有很好的热稳定性。     

Maturity studies and source-rock potential in the southern Sverdrup Basin, Arctic Canada

The purpose of the study is to better understand the relationship between organic matter optical properties and the presence of potentially large oil and gas accumulations in Arctic Canada. The type and thermal maturity of the dispersed organic matter of the Mesozoic formations in the southern Sverdrup Basin, Melville Island, have been studied using organic petrology and Rock-Eval pyrolysis.All types of organic matter are present in the strata of Mesozoic age. Hydrogen-rich liptinite is dominated by alginite (Botryococcus and Tasmanites), dinoflagellate cysts and amorphous fluorescing matrix. Sporinite, cutinite, resinite and liptodetrinite made up the lesser hydrogen-rich exinite. Vitrinite reflectance in Cretaceous sediments ranges from 0.36 to 0.65% R_o; in Jurassic sediments it ranges from 0.40 to 1.0% R_o and in the Triassic from 0.45 to 1.30% R_o, showing an overall increase with depth of burial.Cretaceous sediments of the Deer Bay Formation are thermally immature and contain organic matter of terrestrial origin. The Upper Jurassic shales of the Ringnes Formation contain predominantly organic matter of liptinitic and exinitic origin with a considerable vitrinitic input. At optimum maturation levels, potential source beds of this formation would have a good hydrocarbon-generating potential. The hydrocarbon potential, however, would be limited to the generation of gases due to the leanness of the source rocks. Parts of the Lower Jurassic Jameson Bay Formation are organic-rich and contain a mixed exinitic/vitrinitic organic matter, Botryococcus colonial algae but visible organic matter is dominated by high plant remains (mainly spores). The Schei Point Group shales and siltstones contain organic matter of almost purely marine origin, whereas the predominantly higher plant-derived organic matter found in the Deer Bay, Jameson Bay and partly in the Ringnes formations have higher TOC. Among the Schei Point Group samples, the Cape Richards and Eden Bay members of the Hoyle Bay Formation are richer in TOC (>2.0%) than the Murray Harbour Formation (Cape Caledonia Member). This may reflect differences in the level of maturity or in the depositional environment (more anoxic conditions for the former).Regional variations in the level of thermal maturity of Mesozoic sediments in Sverdrup Basin appear to be a function of burial depth. The Mesozoic formations thicken towards the basin centre (NNE direction), reflecting the general pattern of increasing thermal maturity north of Sabine Peninsula. However, the regional thermal-maturation pattern of the Mesozoic is not solely a reflection of the present-day geothermal gradient, which indicates that anomalous zones of high geothermal gradient may have existed in the past, at least since when the Mesozoic sediments attained maximum burial depth. The contour pattern of the regional variation of maturity at the base of numerous Triassic formations is similar to that of the structural contours of the Sverdrup Basin, indicating that present-day maturation levels are largely controlled by basin subsidence.     

荷载对重塑煤体吸附特性的影响

碎软煤的完整原样制取困难,需要加工制成重塑煤体,为了研究不同压制荷载对煤体物性特征的影响,以重塑煤体为研究对象,基于低温液氮的孔隙测试实验和高压容量法的甲烷吸附实验,探讨不同成型荷载而成的重塑煤体的微小孔结构及其吸附特性的差异。结果表明:不同成型荷载压制而成的重塑煤体,其微孔和小孔的孔容随着成型荷载的增大而略微减少,孔比表面积随着成型荷载的增大而略微增加,总孔体积减少和孔比表面积增加的幅度不大;通过分形理论发现无论高压段还是低压段,孔隙结构具有明显的分形特征,且在高压段的分形维数普遍低于低压段,不同荷载压制而成的重塑煤体的分形维数差别不大;等温吸附线均符合第Ⅰ类等温吸附曲线,Langmuir模型适用于描述重塑煤体的等温吸附,成型荷载对煤的吸附常数有一定的影响,其对吸附常数b值的影响大于对a值的影响。研究不同成型荷载下重塑煤体的吸附特性,为不同条件下型煤制作及冷冻取心实验提供参考。      

Prognostication of hydrocarbon generative potential in the onshore and offshore Niger Delta,Nigeria using TOC content and rock-eval pyrolysis techniques

This article prognosticates the hydrocarbon generation potential of core samples from fields A, B, C and D in Niger delta, Nigeria. The objectives of this study are to characterize the quality of these core samples by organic geochemical analyses. A total of ten core samples collected from fields A, B, C and D in Niger delta were analyzed using total organic carbon （TOC） content analysis, rock-eval pyrolysis technique. The analytical results of the stud- ied core samples reveal that they have generally high total organic carbon contents （TOC）, suggesting that conditions in the Niger delta favour organic matter production and preservation. There is a variation in the kerogen types and this may be attributed to the relative stratigraphic positions of the core samples within the Niger delta. The rock-eval results indicate that the samples from fields C and D contain predominantly Type II kerogen with a capacity to gen- erate oil and gas and hence have good generative potential. The samples from fields A and B contain mainly Type III kerogen and are gas-prone with moderate generative potential.     

Effect of heavy metals and surfactants on the adsorption of phenolic compounds on sediment

The effects of different heavy metals (copper and mercury), cationic surfactants cetylpyridinium chloride, anionic surfactant sodium dodecylbenzenesulfonate and the chemistry of the solution (pH value) on the adsorption of three selected phenolic compounds (2, 4-Dichlorophenol, 2, 4-Dinitro-phenol and 2, 4-Dimethyphenol) on sediment were studied. Results indicated that in the sediment-water system with phenolic compounds: (1) all of the data could be simulated by Freundlich equation; (2) the experiments studying pH effects showed that the adsorption capacity of 2, 4-Dichlorophenol and 2, 4-Dimethyphenol were quite potentia Hydrogenii dependent and increased with decrease in potentia Hydrogenii, while 2, 4-Dinitrophenol followed the different trend; (3) As the concentration increased from 0 to 0.2?mM for Cu²⁺, the Freundlich capacity coefficient constant varied from 62.84 to 325.1 for 2, 4-Dichlorophenol, from 13.1 to 82.179 for 2, 4-Dinitrophenol and from 29.433 to 7.976 for 2, 4-Dimethyphenol, respectively. The Freundlich capacity coefficient constant of 2, 4-Dichlorophenol, 2, 4-Dinitrophenol and 2, 4-Dimethyphenol varied from 62.84 and 421.43, 13.1 and 138.1, 29.433 and 1.381, respectively, with concentration of Hg²⁺ increased from 0 to 0.04?mM, respectively; (4) the adsorption of 2, 4-Dichlorophenol and 2, 4-Dimethyphenol were accentuated by cetylpyridinium chloride but suppressed by sodium dodecylbenzenesulfonate, whereas the adsorption of 2, 4-Dinitrophenol on sediment was enhanced by both cationic and anionic surfactants, effects that are consistent with electrostatic and hydrophobic interactions among ionic surfactants, phenolic compounds and sediment. The results are believed to provide a useful insight into describing the transport and fate of phenolic compounds in natural environments.     

Determination of hydrocarbon generation potential of a non-isothermal pyrolysis of Faraghun and Sarchahan Formations in Coastal Fars and the Persian Gulf,Iran

Source rock assessment is a key step in any petroleum exploration activity. The results of Rock-Eval analysis showed that Sarchahan Formation was in the late oil window, while the Faraghun and Zakeen Formations were just in the early stages of the oil window. Furthermore, Sarchahan, Zakeen and Faraghun Formations exhibited different kerogen types (types-Ⅱ, types-Ⅲ and type-Ⅲ, respectively). Refining the kinetic parameters using the OPTKIN software, the error function returned error values below 0.1, indicating accurate optimization of the kinetic parameters. Based on the obtained values of activation energy, it was clear that Sarchahan Formation contained type-Ⅱ kerogen with an activation energy of 48–52 kcal/mol, while Zakeen and Faraghun Formations contained type-III kerogen with activation energies of 70–80 kcal/mol and 44–56 kcal/mol, respectively. The geographical distribution of the samples studied in this work, it was found that the organic matter (OM) quantity and quality increased as one moved toward the Coastal Fars in Sarchahan Formation. The same trend was observed as one moved from the southern coasts of Iran toward the shaly and coaly portions of Faraghun Formation in the center of the Persian Gulf.©2021 China Geology Editorial Office.     

Effect of organic-matter type and thermal maturity on methane adsorption in shale-gas systems

A series of methane (CH₄) adsorption experiments on bulk organic rich shales and their isolated kerogens were conducted at 35 °C, 50 °C and 65 °C and CH₄ pressure of up to 15 MPa under dry conditions. Samples from the Eocene Green River Formation, Devonian–Mississippian Woodford Shale and Upper Cretaceous Cameo coal were studied to examine how differences in organic matter type affect natural gas adsorption. Vitrinite reflectance values of these samples ranged from 0.56–0.58 %R_o. In addition, thermal maturity effects were determined on three Mississippian Barnett Shale samples with measured vitrinite reflectance values of 0.58, 0.81 and 2.01 %R_o.For all bulk and isolated kerogen samples, the total amount of methane adsorbed was directly proportional to the total organic carbon (TOC) content of the sample and the average maximum amount of gas sorption was 1.36 mmol of methane per gram of TOC. These results indicate that sorption on organic matter plays a critical role in shale-gas storage. Under the experimental conditions, differences in thermal maturity showed no significant effect on the total amount of gas sorbed. Experimental sorption isotherms could be fitted with good accuracy by the Langmuir function by adjusting the Langmuir pressure (P_L) and maximum sorption capacity (Γ_max). The lowest maturity sample (%R_o = 0.56) displayed a Langmuir pressure (P_L) of 5.15 MPa, significantly larger than the 2.33 MPa observed for the highest maturity (%R_o > 2.01) sample at 50 °C.The value of the Langmuir pressure (P_L) changes with kerogen type in the following sequence: type I > type II > type III. The thermodynamic parameters of CH₄ adsorption on organic rich shales were determined based on the experimental CH₄ isotherms. For the adsorption of CH₄ on organic rich shales and their isolated kerogen, the heat of adsorption (q) and the standard entropy (Δs⁰) range from 7.3–28.0 kJ/mol and from −36.2 to −92.2 J/mol/K, respectively.     

Effect of surface oxidation and iron contents on xanthate ions adsorption of synthetic sphalerites

Abstraction of xanthate ions from solution by copper-activated synthetic sphalerites with various iron contents was measured. It was found that raising the iron content in the samples caused a decrease in xanthate ions abstraction. For sphalerite samples characterized by the same percentage of iron deoxidized surfaces took up more xanthate ions than oxidized surfaces.Surface coverage by EtX^? ions was determined to be less than one monolayer. These values were compared with copper ion coverage at sphalerite surface. The amount of EtX^? ions abstracted from solution was noted to be independent of the pH of the solution in the range from 6 to 10 pH units, above $\text{pH}\text{=10}$ a decrease in the abstraction was observed.     

剪切作用对页岩有机质孔发育特征和吸附能力的影响

有机质孔是高成熟页岩储层中吸附气和游离气赋存的主要储集空间类型。中国南方海相页岩地层经历了多期构造改造,滑脱构造广泛发育。为了认识剪切作用对页岩有机质孔微观结构和吸附能力的影响,以张家界三岔地区下寒武统牛蹄塘组页岩为例,通过大量扫描电镜图像观测统计,对比分析了滑脱带页岩、邻近滑脱带页岩和远离滑脱带页岩有机质孔的发育特征,同时对这三类样品进行了甲烷等温吸附测试。研究结果表明,有机质内孔发育在有机质内部,孔径一般＜20 nm;位于有机质与矿物接触边缘的复合孔孔径整体大于有机质内孔,主要发育在滑脱带页岩中包裹有矿物碎片的有机质中。受剪切作用影响,这两类有机质孔均沿一定优势方向发生形变,形态更趋于狭长且定向性增强;同时页岩甲烷吸附能力变差,从滑脱带向远离滑脱带方向这种影响逐渐减弱。剪切作用对页岩储集性能和含气性具有重要控制作用,对认识复杂构造区页岩气保存条件和富集规律具有重要意义。      

Effect of groundwater fulvic acid on the adsorption of arsenate by ferrihydrite and gibbsite

Adsorption studies have been conducted at pH 4, 6 and 8 to assess the effect of fulvic acid on arsenate adsorption to ferrihydrite and gibbsite. The studies compared the adsorption of arsenate on the mineral surfaces in the absence of fulvic acid, to those cases where increasing concentrations of fulvic acid (0.3–60 μM) were added to the mineral–arsenate suspensions. Experiments where arsenate was added to mineral–fulvate suspensions were also conducted. The results suggest that arsenate adsorption on both gibbsite and ferrihydrite decreases with increasing concentrations of fulvic acid. This effect was highest at pH 4, and decreased at pH 6 and 8. Ferrous ion concentrations were very low during the ferrihydrite experiments and support the view that fulvic acid can both displace arsenate from and inhibited its adsorption to mineral surfaces. The experiments also indicated that the amount of arsenate adsorbed was lower if fulvic acid was added before rather than after arsenate. This may reflect the relative size of arsenate and fulvic acid molecules and their ability to penetrate the crystal matrices of the minerals.     

烃、汞等气体组分垂向运移的主要控制因素

本文从断层与裂隙、盖层的封堵性、异常源的浓度差与压力差、各组分的地球化学性状与行为四大方面讨论了其对油气藏中烃类、汞等气体组分垂向运移的控制作用，并进一步说明了其是地表各类油气化探异常分布规律、形态和异常模式构成的主要因素。