Gaseous hydrocarbons generated during pyrolysis of petroleum source rocks using unconventional grain-size: implications for natural gas composition

Open-system pyrolysis experiments were performed on a suite of immature to marginally mature source rocks to investigate the influence of kerogen type on primary gas composition and the effect of grain size on gas expulsion characteristics. The pyrolysis of rock powders confirmed that hydrogen-rich kerogens yielded wetter gases than did hydrogen-poor kerogens. Gases detected from the pyrolysis of rock chips were drier than those from powders of equivalent samples. This was due to two processes: the retention and secondary cracking of higher molecular weight pyrolysis products and the preferential expulsion of methane from the rock matrix. These two effects, one chemical the other physical, could be distinguished using a novel approach involving multi-step pyrolysis of rock chips followed by on-line crushing of the residues. The enrichment of methane in natural gas attributed, by earlier workers, to be a consequence of fractionation during secondary migration (post-expulsion) has been proven to be real also during expulsion from source rocks at least for pyrolysis conditions.     

我国酸沉降地区硫源的硫同位素组成研究

我国同世界大部分地区的酸雨类型一致,均为典型的硫酸型酸雨,因此硫同位素组成是示踪酸雨来源的重要手段。在前人研究的基础上,对酸雨硫同位素组成研究的思路和实验方法进行综述,重点介绍燃煤过程中硫同位素的分馏效应和大气SO2、气溶胶、大气降水、苔藓和小麦等植物中的硫同位素组成等,对环境地球化学的研究具有重要意义。     

Stable sulfur isotope partitioning during simulated petroleum formation as determined by hydrous pyrolysis of Ghareb Limestone, Israel

Hydrous pyrolysis experiments at 200 to 365°C were carried out on a thermally immature organic-rich limestone containing Type-IIS kerogen from the Ghareb Limestone in North Negev, Israel. This work focuses on the thermal behavior of both organic and inorganic sulfur species and the partitioning of their stable sulfur isotopes among organic and inorganic phases generated during hydrous pyrolyses. Most of the sulfur in the rock (85%) is organic sulfur. The most dominant sulfur transformation is cleavage of organic-bound sulfur to form H₂S_(gas). Up to 70% of this organic sulfur is released as H₂S_(gas) that is isotopically lighter than the sulfur in the kerogen. Organic sulfur is enriched by up to 2‰ in ³⁴S during thermal maturation compared with the initial δ³⁴S values. The δ³⁴S values of the three main organic fractions (kerogen, bitumen and expelled oil) are within 1‰ of one another. No thermochemical sulfate reduction or sulfate formation was observed during the experiments. The early released sulfur reacted with available iron to form secondary pyrite and is the most ³⁴S depleted phase, which is 21‰ lighter than the bulk organic sulfur. The large isotopic fractionation for the early formed H₂S is a result of the system not being in equilibrium. As partial pressure of H₂S_(gas) increases, retro reactions with the organic sulfur in the closed system may cause isotope exchange and isotopic homogenization. Part of the δ³⁴S-enriched secondary pyrite decomposes above 300°C resulting in a corresponding decrease in the δ³⁴S of the remaining pyrite. These results are relevant to interpreting thermal maturation processes and their effect on kerogen-oil-H₂S-pyrite correlations. In particular, the use of pyrite-kerogen δ³⁴S relations in reconstructing diagenetic conditions of thermally mature rocks is questionable because formation of secondary pyrite during thermal maturation can mask the isotopic signature and quantity of the original diagenetic pyrite. The main transformations of kerogen to bitumen and bitumen to oil can be recorded by using both sulfur content and δ³⁴S of each phase including the H₂S_(gas). H₂S generated in association with oil should be isotopically lighter or similar to oil. It is concluded that small isotopic differentiation obtained between organic and inorganic sulfur species suggests closed-system conditions. Conversely, open-system conditions may cause significant isotopic discrimination between the oil and its source kerogen. The magnitude of this discrimination is suggested to be highly dependent on the availability of iron in a source rock resulting in secondary formation of pyrite.     

Evaluation of the petroleum composition and quality with increasing thermal maturity as simulated by hydrous pyrolysis: A case study using a Brazilian source rock with Type I kerogen

Hydrous pyrolysis (HP) experiments were used to investigate the petroleum composition and quality of petroleum generated from a Brazilian lacustrine source rock containing Type I kerogen with increasing thermal maturity. The tested sample was of Aptian age from the Araripe Basin (NE-Brazil). The temperatures (280–360 °C) and times (12–132 h) employed in the experiments simulated petroleum generation and expulsion (i.e., oil window) prior to secondary gas generation from the cracking of oil. Results show that similar to other oil prone source rocks, kerogen initially decomposes in part to a polar rich bitumen, which decomposes in part to hydrocarbon rich oil. These two overall reactions overlap with one another and have been recognized in oil shale retorting and natural petroleum generation. During bitumen decomposition to oil, some of the bitumen is converted to pyrobitumen, which results in an increase in the apparent kerogen (i.e., insoluble carbon) content with increasing maturation.The petroleum composition and its quality (i.e., API gravity, gas/oil ratio, C₁₅₊ fractions, alkane distribution, and sulfur content) are affected by thermal maturation within the oil window. API gravity, C₁₅₊ fractions and gas/oil ratios generated by HP are similar to those of natural petroleum considered to be sourced from similar Brazilian lacustrine source rocks with Type I kerogen of Lower Cretaceous age. API gravity of the HP expelled oils shows a complex relationship with increasing thermal maturation that is most influenced by the expulsion of asphaltenes. C₁₅₊ fractions (i.e., saturates, aromatics, resins and asphaltenes) show that expelled oils and bitumen are compositionally separate organic phases with no overlap in composition. Gas/oil ratios (GOR) initially decrease from 508–131 m³/m³ during bitumen generation and remain essentially constant (81–84 m³/m³) to the end of oil generation. This constancy in GOR is different from the continuous increase through the oil window observed in anhydrous pyrolysis experiments. Alkane distributions of the HP expelled oils are similar to those of natural crude oils considered to be sourced from similar Brazilian lacustrine source rocks with Type I kerogen of Lower Cretaceous age. Isoprenoid and n-alkane ratios (i.e., pristane/n-C₁₇ and phytane/n-C₁₈) decrease with increasing thermal maturity as observed in natural crude oils. Pristane/phytane ratios remain constant with increasing thermal maturity through the oil window, with ratios being slightly higher in the expelled oils relative to those in the bitumen. Generated hydrocarbon gases are similar to natural gases associated with crude oils considered to be sourced from similar Brazilian lacustrine source rocks with Type I kerogen of Lower Cretaceous, with the exception of elevated ethane contents. The general overall agreement in composition of natural and hydrous pyrolysis petroleum of lacustrine source rocks observed in this study supports the utility of HP to better characterize petroleum systems and the effects of maturation and expulsion on petroleum composition and quality.     

盐城凹陷烃源岩分析及成藏期次研究

应用碳同位素及天然气成熟度经验公式分析气源,确定了天然气成因类型以油型气为主,主力烃源岩层位为上古生界栖霞组。分析该区烃源岩埋藏史类型发现存在晚期深埋型、两期深埋型和早期深埋型三种类型,晚期深埋型最有利于油气二次成藏。对该区流体包裹体有机质丰度及均一化温度分析发现盐城凹陷有过两期油气充注,时间为晚始新世—新第三纪期间的5Ma～11Ma和32Ma～34Ma,以晚期充注成藏为主要特征。     

The influence of marine and terrestrial source material on the composition of petroleum

This paper consists of two interrelated parts. In the first part, the influence of the composition of sediment organic matter on crude oil composition is discussed. The second part deals with the origin of normal paraffins in petroleum.Source beds with abundant terrestrial plant matter generate heavy hydrocarbons rich in five-ring naphthenes. Unless such source beds are exposed to a high temperature for a prolonged time, the oils released are also rich in five-ring naphthenes. Such oils are rare; thus far the only examples found are some Eocene Wilcox oils from the Texas Gulf Coast and some Eocene Green River oils from the Uinta Basin, Utah. Normally, oil source beds are not rich in terrestrial plant matter and the five-ring naphthene content of the source bed hydrocarbons, as well as that of the produced oils, is low.The n-paraffins generated by oil source beds rich in terrestrial plant matter are characterized by abnormally low (C₂₁ + C₂₂)/(C₂₈ + C₂₉) ratios of 0.6–1.2. In oils of dominantly marine origin, this ratio is in the range 1.5–5.0. The ratio of marine to terrestrial organic matter in source beds appears to influence both the naphthene composition and the n-paraffin composition of the generated oils.Evidence is presented that petroleum n-parainns originate from slow thermal cracking of fatty acids contained in fats and waxes. Reaction equations are discussed which explain the major geochemical observations, including the difference in carbon-number distribution of the assumed parental fatty acids and of their descendant n-paraffins. In normal oils, which originate mostly from fat rich marine organic matter, the n-paraffin concentration tapers off above C₂₀. The molecular weight range of the fatty acids of plant waxes is considerably higher than that of fats. If plant waxes contribute strongly to the oil source material, the molecular weight distribution of the petroleum n-paraffins formed is abnormal and high carbon numbers in the C₂₄-C₃₂ range dominate.     

造缝产烃还是改质造烃？——论含油气源岩层系的储集层属性和烃源岩属性

源岩层系油气已成为世界油气工业体系中举足轻重的重点领域，未来发展潜力很大。本文通过深入解读含油气源岩层系的地质形成条件，发现储集层属性和烃源岩属性在根本上决定了源岩层系油气成功开发的技术路径。储集层属性是指储集层储存和渗滤油气的物理性质及其相互关系，地史时期微—纳米级孔- 喉- 缝系统充注和聚集了大面积连续型油气资源，人工压裂形成缝网系统突破了致密储层的连通属性短板，成功开发了规模油气资源，突破流动属性短板可能是另一个发展方向。烃源岩属性是指烃源岩滞留、转化和排出油气的物理化学性质及其相互关系，包括已转化的滞留油气和未转化的残留有机质，滞留及潜在烃类资源规模巨大，地下人工加热等方式理论上可突破烃源岩的有机质数量和成熟度属性短板，可能是实现成功开发的有效路径。储集层属性和烃源岩属性是实现源岩层系油气规模发展的内在潜质基础，公共属性参数是外部环境基础。造缝产烃还是改质造烃？前提是准确研判优选何种内在属性参数，基础是系统整合优化所有外在属性参数，推动实现源岩层系油气商业化可持续发展，未来中低熟富有机质页岩及油页岩、中高熟富气态烃页岩层系、低变质程度富油煤岩、深层可气化煤炭等是值得期待的战略发展领域。     

Analysis of relationships between geochemical parameters of petroleum potential in related source and carbonaceous materials

A worldwide data set of 1,085 samples containing organic matter of the type II/III kerogen from Carboniferous to Cenozoic was used to analyse the evolution of the hydrogen index (HI), quality index (QI), and bitumen index (BI) with increasing thermal maturity. The HI_max, QI_max and BI_max lines were defined, based on statistical analysis and cross-plots of HI, QI and BI versus the vitrinite reflectance (%Ro) and T _max (°C). The constructed HI, QI and BI bands were broad at low maturities and gradually narrowed with increasing thermal maturity. The petroleum generation potential is completely exhausted at a vitrinite reflectance of 2.0–2.2 % and T _max of 510–520 °C. An increase in HI and QI suggests extra petroleum potential related to changes in the structure of the organic material. A decline in BI signifies the start of the oil window and occurs within the vitrinite reflectance range 0.75–1.05 % and T _max of 440–455 °C. Furthermore, petroleum potential can be divided into four different parts based on the cross-plot of HI versus %Ro. The area with the highest petroleum potential is located in “Samples and methods” with %Ro = 0.6–1.0 %, and HI > 100. Oil generation potential is rapidly exhausted at “Results and discussion” with %Ro > 1.0 %. This result is in accordance with the regression curve of HI and QI with %Ro based on 80 samples with %Ro = 1.02–3.43 %. The exponential equation of regression can thus be achieved: HI = 994.81e^?1.69Ro and QI = 1,646.2e^?2.003Ro (R ² = 0.72). The worldwide organic material data set defines two range of oil window represented by the upper and lower limits of the BI band: %Ro 0.75–1.95 %, T _max 440–525 °C, and %Ro 1.05–1.25 %, T _max 455–465 °C, respectively.     

不同赋存状态油裂解条件及油裂解型气源灶的正演和反演研究

油裂解型气源灶是一种特殊的气源灶,是优质生烃母质在成气过程中派生出的。烃源岩生成的油主要有3种赋存形式:源内分散状液态烃、源外分散状液态烃和源外富集型液态烃。3种赋存状态液态烃的数量及分配比例受内因和外因多种因素控制,就排油率而言,有机碳含量分别为0.67%、0.62%和10.6%的泥岩、灰岩和油页岩,最大排油率分别为45%、55%和80%。原油与不同介质配样的生气动力学实验表明,不同介质条件下甲烷的生成活化能分布有差异,碳酸盐岩对油裂解条件影响最大,可大大降低其活化能,导致原油裂解热学条件降低,体现为油裂解温度的降低;泥岩次之,砂岩影响最小。碳酸盐岩、泥岩和砂岩对油的催化裂解作用依次减弱,不同介质条件下主生气期对应的Ro值:纯原油1.5%～3.8%;碳酸盐岩中的分散原油1.2%～3.2%;泥岩中的分散原油1.3%～3.4%;砂岩中的分散原油1.4%～3.6%。油裂解型气源灶是一种中间体,可以直观看到的是原生气源灶和由此形成的气藏,而对油裂解型气源灶的赋存形式、分布范围、成气数量和储量规模等问题,只能通过正演和反演的研究去确定且相互映证。正演研究以塔里木盆地中下寒武统为例,原始生油量2232.24×108t,剩余油量806.21×108t,油裂解气量106.95×1012m3。反演研究以川东北飞仙关组白云岩中油裂解气为例,圈定的古油藏面积约735km2,古油藏原油数量45×108t,油裂解气量及油裂解气资源量分别为2.72×1012m3和1.36×1012m3。     

不同赋存态油裂解条件及油裂解型气源灶的正演和反演研究

油裂解型气源灶是一种特殊的气源灶,是优质生烃母质在成气过程中派生出的.烃源岩生成的油主要有3种赋存形式源内分散状液态烃、源外分散状液态烃和源外富集型液态烃.3种赋存状态液态烃的数量及分配比例受内因和外因多种因素控制,就排油率而言,有机碳含量分别为0.67%、0.62%和10.6%的泥岩、灰岩和油页岩,最大排油率分别为45%、55%和80%.原油与不同介质配样的生气动力学实验表明,不同介质条件下甲烷的生成活化能分布有差异,碳酸盐岩对油裂解条件影响最大,可大大降低其活化能,导致原油裂解热学条件降低,体现为油裂解温度的降低;泥岩次之,砂岩影响最小.碳酸盐岩、泥岩和砂岩对油的催化裂解作用依次减弱,不同介质条件下主生气期对应的Ro值纯原油1.5%～3.8%;碳酸盐岩中的分散原油1.2%～3.2%;泥岩中的分散原油1.3%～3.4%;砂岩中的分散原油1.4%～3.6%.油裂解型气源灶是一种中间体,可以直观看到的是原生气源灶和由此形成的气藏,而对油裂解型气源灶的赋存形式、分布范围、成气数量和储量规模等问题,只能通过正演和反演的研究去确定且相互映证.正演研究以塔里木盆地中下寒武统为例,原始生油量2 232.24×108t,剩余油量806.21×108t,油裂解气量106.95×1012m3.反演研究以川东北飞仙关组白云岩中油裂解气为例,圈定的古油藏面积约735 km2,古油藏原油数量45×108t,油裂解气量及油裂解气资源量分别为2.72×1012 m3和1.36×1012 m3.     

Organic matter maturation under the influence of a deep intrusive heat source: A natural experiment for quantitation of hydrocarbon generation and expulsion from a petroleum source rock (Toarcian shale, northern Germany)

Four shallow boreholes were drilled in the Hils syncline, northern Germany, in order to determine quantitatively the amount of hydrocarbons generated and expelled during maturation of a typical kerogen-type-II-bearing source rock. The holes penetrated the carbonceous Lias shales (Posidonia shale, Lower Toarcian) and part of the adjacent Dogger α and Lias δ mudstones. The maturity of the organic matter in the cores recovered ranges from immature (0.48% R̄₀) to overmature 1.45% R̄₀) due to location of the Hils syncline in the vicinity of the Vlotho Massif, which is deep-seated intrusive body. Facies variations of the Lias within the short geographical distances in the study area are negligible.Organic matter mass balance calculations were based on detailed organic geochemical analyses of residual material in the Lias shales (kerogen, bitumen etc.) and on the evidence of a uniform initial composition of these sediments in the study area. Dead carbon determinations supported this latter criterion but were not used as a parameter in the calculations.About 50% of the initial kerogen was transformed into oil, gas and inorganic compounds during the vitrinite reflectance increase from 0.48 to 0.88% R̄_o and only marginally more during the maturity increase from 0.88 to 1.45% R̄_o. Only a small portion of the generated material remained in the source rock even at a relatively early stage of generation (0.68% R̄_o). Expulsion efficiency of oil plus gas reached a value of 86% at the end of the main generation stage (0.88% R̄_o).     

Water／Rock Interactions and Changes in Chemical Composition During Zeolite Mineralization

Systematic analysis and comparative study of the chemical compositons of rocks and ores from the main types of zeolite deposits in the surroundings of the Songliao Basic have shown that the process of formation of zeolite from volcanic and pyroclastic rocks is generally characterized by the relative purification of SiO2,i.e.,SiO2/Al2O3 ratios tend to increase,alkali eart elements (CaO MgO)and H2O are relatively enriched,and the alkali metals(K2O Na2O)are depleted in their total amount.The alkali metals K and Na follow different rules of migration and enrichment during the formation of mordenite and clinoptilolite.In the process of formation of mordenite more Na^ will be imported and K^ will be lost remarkably.On the contrary,in the process of formation clinoptilolite more K^ will be incorporated and Na^ will become obviously depleted.     

Structure proof and significance of stereoisomeric 28,30-bisnorhopanes in petroleum and petroleum source rocks

Two C₂₈H₄₈-pentacyclic triterpanes were isolated from Monterey shale. X-ray crystallography of a crystal containing both compounds proved their structures as 17β,18α,21α(H)-28,30-bisnorhopane and 17β,18α,21β(H)-28,30-bisnorhopane. Several differences are found between 28,30-bisnorhopanes and the regular hopanes. Unlike the regular hopane epimers, for practical purposes the three epimeric 28,30-bisnorhopanes [17α,21β(H)-, 17β,21α(H)-, and 17β,21β(H)-]cannot be distinguished by their mass spectra. Special conditions are needed to separate them by gas chromatography. The diagenetically first-formed epimer is thought to be 17α,21β(H)- because it predominates in immature shales. The order of thermodynamic stability is 17β,2lα(H) < > 17α,21β(H) > 17β,21β(H), and all three epimers are present in petroleum. 25,28,30-Trisnorhopanes can be analyzed in similar fashion and are found to have similar thermodynamic characteristics. The percent of the ring D/E cis epimer of 28,30-bisnorhopane and/or 25,28,30-trisnorhopane is a useful maturation parameter similar to the 20S/20R sterane ratio. Evidence indicates 25-demethylation of 28,30-bisnorhopane to 25,28,30-trisnorhopane during advanced stages of biodegradation. Hence, percent ring $\text{D}\text{E}$cis 25,28,30-trisnorhopane has an application to maturation assessment in heavily biodegraded oils.     

Catagenesis and composition of petroleum: Origin of n-alkanes and isoalkanes in petroleum crudes

Distribution of n-alkanes and isoalkanes in ca. 50 petroleum crudes have been examined by the gas chromatography. Molar distributions of n-alkanes with respect to their c atom numbers in the majority of crudes follow the exponential law, which signifies a random, chemical nature of n-alkane-generating processes occurring in the catagenesis stage of petroleum maturation. Similar distributions of n-alkanes were found in the products of mild thermolysis of heavy n-alkanes.Isoalkanes represent a major, 10–25%, petroleum component. The principal types of isoalkanes in crudes are monomethyl-branched, with the branches randomly positioned in the chains, and dimethyl-branched with one of the methyl groups predominantly in the second position in the chains. Thermolysis studies of individual n-alkanes, alkanoic acids, and esters in the presence of various minerals provided an explanation of the n-alkane and isoalkane distributions. Selected heavy n-alkanes are initially formed in decarboxylation reactions of heavy n-alkanoic acids and esters. Extensive thermocracking produces mixtures of lighter n-alkane and α-olefins. The olefins, in the presence of acidic clays, are converted in cationic reactions into mixtures of predominantly mono- and dimethyl-branched isoalkanes.     

川中广安气田天然气成因类型及气源分析

川中广安气田是四川盆地2006年新发现的上报探明地质储量超过500×108m3的大型气田,也是目前四川盆地在上三叠统产层发现的最大气田。由于广安气田所在地区上三叠统烃源岩的生气强度小于20×108m3/km2,不具备形成大中型气田的理想条件,因此该气田的天然气成因类型及气源成为一个亟待解决的问题。笔者通过对广安气田天然气组分和碳同位素等资料的详细分析,判定其天然气为煤成气;根据气源对比,排除了下伏和上覆烃源岩的供源可能性,证实广安气田为上三叠统须家河组煤系地层自生自储形成。最后,经过对天然气运移途径分析,认为近源侧向运移是形成广安大型气田的主因。     

Changes in carbon and oxygen isotope composition during limestone diagenesis

The calcite fossils of the Derbyhaven Beds, Isle of Man, have δ¹³C values (+ 1·8 PDB) similar to modern, shallow-water marine skeletons, but the δ¹⁸O values (?6·1 PDB) are much lighter than modern skeletons. The light oxygen values indicate either re-equilibration with isotopically light water before cementation started, or Carboniferous sea water with δ¹⁸O of ?6‰. Aragonite dissolution was followed by precipitation of zoned calcite cement. In this cement, up to six intracrystalline zones, recognized in stained thin sections, show isotopic variation. Carbon varies from + 3-8 to + 1-2‰. and oxygen from ? 2-6 to ? 12-4‰. with decreasing age of the cement. This trend is attributed to increasing temperature and to isotopic evolution of the pore waters during burial. The zoned calcite is sequentially followed by dolomite and kaolinite cements which continue the trend towards light isotopic values. This trend is continued with younger, fault-controlled dolomite, and is terminated by vein-filling calcite and dolomite. The younger calcite, interpreted as a near-surface precipitate from meteoric waters, is unrelated to the older sequence of carbonates and has distinctly different carbon isotope ratios: δ¹³C ? 6-8‰.     

济阳坳陷石炭二叠系埋藏条件及煤型气源岩分布特征

山东地区经历了多次构造运动,含煤地层遭受严重破坏,因此各地煤系保存程度差异较大。济阳坳陷是石炭—二叠系的深陷区,但济阳坳陷构造十分复杂,煤系保存于坳陷中的一些次级凹陷中。石炭二叠系的埋深多在30 0 0~5 0 0 0m范围内,次级凹陷局部出现较大的埋深变化,最大埋深可达上万米,最小埋深仅在千米左右。煤型气源岩主要为煤层和暗色泥质岩。泥质岩最厚为5 5 5.5m (惠民凹陷),煤层最厚4 0.5m (车镇凹陷),泥岩、煤层厚度分布与残留厚度的变化趋势大体一致。研究表明,济阳坳陷石炭二叠系煤层属较好的烃源岩,泥岩整体上为差—中等烃源岩,局部发育有好的烃源岩。