海相原油沥青质作为特殊气源的生气特征及其地质应用

应用高压封闭体系,对塔里木盆地海相原油中的沥青质组分进行了热裂解模拟实验,从气态烃产率及碳同位素演化、焦沥青的生成等方面,探讨了沥青质作为特殊气源的生气机理。运用Kinetics动力学软件,计算得到沥青质裂解的动力学参数（活化能和指前因子）,在此基础上,将模拟实验结果外推至地质条件下,探讨其动力学模型的实际应用。结果表明,沥青质裂解气在Easy%Ro值0.8左右开始生成,在Easy%Ro值2.65左右其转化率达到1。Easy%Ro为0.9时沥青质裂解进入主生气期（转化率0.1）,Easy%Ro为2.3时主生气期结束（转化率0.9）。研究成果可为中国海相层系裂解气的判识、资源评价及勘探决策等提供实验和理论依据。     

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.     

寒武系烃源古油藏油裂解气特征及成藏条件

在寒武系为母源的气藏中,普遍存在的固体沥青、25-降藿烷、氮气等三种物质,实际是古油藏残余油裂解的产物。25-降藿烷一般与氧化—降解油有关,氮气来自油藏水洗时溶入的大气,二者共同反映古油藏经历的抬升破坏作用。寒武系烃源一般经历过两次成藏:加里东—海西期形成“油藏”,燕山—喜马拉雅期裂解为“气藏”。寒武系油裂解气成藏的地质条件是:古构造聚油、后期改造适度、叠合盆地增熟、断层作为油气运移通道等。围绕加里东—海西期古油藏寻找原生、次生油裂解气是今后寻找寒武系来源油气的重要途径。     

Carbon isotope geochemistry of Paleozoic oils from Big Horn Basin

Twenty crude oils from Paleozoic reservoirs in the Big Horn Basin. Wyoming were fractionated into light hydrocarbons, saturates, monoaromatics. diaromatics, polyaromatics-and-polars. and asphaltenes. Amounts and isotopic composition of each fraction were found to be internally consistent with the degree of maturation of the oil. confirming the established single source origin for these oils. A variation of approximately three per mil in the carbon isotopic composition of the whole oil and individual fraction was explained as being caused by maturation. The isotope-type-curves for these oils, the variations in isotopic composition as a function of compound group-type, were not found to be as simple as commonly believed. Other alteration processes, such as migration and deasphalting, might have influenced the pattern of the isotope distributions among fractions. The conservative nature of mass balance and subsequent isotope flows among various fractions of crude oil showed that the maturation of crude oil consists of consecutive processes leading from larger and more polar components into smaller and less polar components culminating in natural gas. Calculations were made to project the amount of condensates associated with the crude oils, and the amount of natural gas which had been generated from crude oils of a given maturity.     

雅克拉凝析气田油气地球化学特征

雅克拉凝析气田天然气组分以甲烷为主,含量79.13%￣89.30%;重烃含量较高,平均占9.67%;干燥系数(C1/C1-5)介于0.89～0.92之间,属典型的湿气。δ13C1为-40.8‰～-39.4‰,δ13C2为-32.0‰～-30.2‰,δ13C3为-30.5‰～-28.9‰,表明天然气为典型的油型气。原油及其族组分的碳同位素组成和生物标志化合物呈现出典型的海相原油特征。原油成熟度较高,与天然气的成熟度基本相同,表明油气同源、同阶,为一次油气充注的产物,而与塔河油田存在较大差异。     

原油极性组分的吸附与储层润湿性及研究意义

探讨了原油极性组分（非烃,沥青质）的吸附机理及其吸附性,润湿性特征;介绍了ＮＳＯ极性化合物与润湿性的关系。极性化合物的吸附可能是多种机理共同作用的结果,吸附作用可导致储层润湿性反转,润湿性是决定原油采收集的主要因素。通过改变储层润湿性,可能有利于提高原油采收率。极性化合物的吸附等特性在储层润湿性研究,油田开发管理中具有重要意义。     

The isotopic composition of carbon in the Alberta oil sand

The carbon isotopic ratios obtained from Athabasca bitumen, asphaltene and maltene have the same value $\text{δ}{}^{13}\text{C}\text{= ?29.6}\text{per ml}$. The corresponding values in the Cold Lake deposits are ?30.6, ?30.0 and ?31.6 per ml. The ratios determined for methane collected from the oil sand and its fractions are about 15 per ml lower than the above values. It appears that the Athabasca and Cold Lake Reservoirs have similar histories.     

Geochemical characteristics of the macromolecular part of crude and biodesulphurised flame coal density fractions

Flame coal (Janina Mine, Poland) was an object of geochemical analyses for changes caused by the process of microbial desulphurisation. Ash content, beryllium, chromium, zinc, cobalt, lithium, manganese, copper, molybdenum, nickel, lead and vanadium concentrations were investigated in coal extracts, its macromolecular part, semi-coke and polar compound fractions of extracts and pyrolysates of crude and biodesulphurised coal density fractions. The macromolecular part of extracted density fractions was pyrolysed giving semi-coke and pyrolysate. These were separated into aliphatic hydrocarbons, aromatic and polar compounds by thin layer chromatography (TLC). Distributions of aliphatic and aromatic hydrocarbons in pyrolysates of the crude and desulphurised coal density fractions were compared by gas chromatography-mass spectrometry (GC-MS). Extracts, extracted density fractions, semi-coke and polar compound fractions were analysed for concentrations of trace elements. In the crude coal their concentrations in the macromolecular part are related only to coke. However, in the desulphurised coal the participation of the particular trace element increases in pyrolysate polar compound fractions. Its values are in the range from 1% (Mn) to 100% (Cr and Mo). These changes are the best seen in the 1.80-2.30×10³ kg/m³ density fraction. Very high concentrations of trace elements were found in pyrolysate of desulphurised coal density fraction. This can be explained by the partial decomposition of coal macromolecule resulting from desulphurisation. Significant side-cleavage of peripheral groups and lighter aromatic hydrocarbons is possible. The effects of bacterial influence were manifested by the increase of polar compounds contents both in pyrolysates and extracts of the desulphurised coal and changes in distribution of aliphatic and aromatic hydrocarbon as pyrolytical products. These effects increase with mineral substance contents. Moreover, the increase of trace element concentration in coal organic matter occurs. It is reflected by the increase of participation of coal pyrolysate polar fraction in the total concentration of analysed elements in the macromolecular part of a given density fraction. The presented results are a part of the larger research aimed to find an influence of desulphurisation on chemical and technological properties of coal.     

南羌塘鄂斯玛地区早白垩世沥青地球化学特征及意义

首次在南羌塘安多县鄂斯玛地区早白垩世地层中发现沥青。从沥青有机碳含量、族组分及生物标志化合物方面综合研究了其有机地球化学特征,并进行了油源对比。研究结果表明,样品的有机碳含量为3.42%~75.01%,显示其有较高的沥青含量;族组成中重烃组分(非烃+沥青质)质量分数最高,其次为芳香烃,饱和烃质量分数最低。生物标志物研究表明,沥青的成熟度较高,沥青母岩的沉积环境为还原环境,其有机母质主要为混合来源,特别是藻类做出了重要贡献。运用生物标志化合物的相对含量指标进行油源对比研究表明,沥青可能来源于索瓦组泥岩。该研究成果对南羌塘的油气勘探具有一定意义。     

生排烃过程中正构烷烃单体碳同位素组成的变化特征及其研究意义

通过对生排烃模拟实验产物 (残留油和排出油 )中正构烷烃单体碳同位素组成的测定,揭示出生排烃过程中正构烷烃碳同位素组成的变化特征。研究表明,生烃初期,液态正构烷烃主要来自干酪根的初次裂解,它们的碳同位素组成不论是在排出油中还是在残留油中,随温度的变化都不明显,呈现较相似的分布特征;在生烃高峰期,早期形成的沥青质和非烃等组分的二次裂解以及高碳数正构烷烃可能存在的裂解,使得正构烷烃单体碳同位素组成明显富集13 C,尤其在高碳数部分呈现出较大的差异。另外,实验结果显示排烃作用对液态正烷烃单体碳同位素组成的影响不太显著。     

低成熟油页岩的生排烃作用实验模拟

烃源岩的成熟演化特征对评价一个区域的油气产出背景意义重大。笔者选择准噶尔南部低熟油页岩作为试验样品,分别进行无水变温、等温变水及等水变温条件下的烃源岩热模拟实验,并依据油、气、固体残渣的定性定量检测,分析烃类相态与组成变化。得到以下结果:无水变温及等水变温实验中油产率均在300 ℃时出现最高值,而且在等水变温情况下,200 ℃时的产油率比不加水情况下明显增大;在等温变水情况下,生油量在加10 mL水时最大;干气生成阶段,气态烃主要来自重烃裂解而不是高度演化的干酪根本身,400 ℃热解之后,剩余生烃率大约为5％左右;饱和烃在低温和极端高温时相对比例高,以正构烷烃为绝对优势组分;芳烃比例变化波动较大,以三环、四环芳烃为主,在400 ℃时达到最大值,在500 ℃时跌至最低值;非烃、沥青质相对比例变化与芳烃正好相反。     

Field-ionization mass spectrometry: application to geochemical analysis

The thiourea adduct, thiourea non-adduct and aromatic fractions from a series of Alberta oil sand bitumens have been subjected to field ionization mass spectrometric analyses. Field ionization mass spectra feature little fragmentation and the molecular weight distributions of compounds in the fractions are readily obtained. Using this method, the various acyclic and cyclic saturated hydrocarbons and the hydrocarbon and thiophenic aromatic materials may be distinguished by compound type and number of carbon atoms. The effect of biodegradation on crude oils is illustrated in the results from the series of oil sand bitumens and their asphaltene pyrolysis products. Field ionization mass spectrometry is potentially an important new analytical tool in organic geochemistry.     

川东北飞仙关组储层固体沥青地球化学特征及其气源指示意义

运用有机岩石学、有机地球化学、催化加氢热解、GC—IRMS等方法和技术,深入研究了川东北飞仙关组储层固体沥青及可能烃源岩的地球化学特征。研究认为,飞仙关组储层固体沥青反射率高,双反射明显,为非均质结构储层焦沥青;在碳酸盐岩储层的各种孔隙中,呈脉状、球粒状、角片状或块状等他形充填,具有中间相结构和镶嵌状结构特征,反映其高温热变质成因;元素组成有S/C高、H/C低的特点,其固体碳同位素组成与长兴组烃源岩干酪根相似。储层固体沥青的可能烃源岩发育于还原—弱氧化咸水沉积环境,有机质来源于水生藻类;氯仿沥青“A”饱和烃甾萜类生物标志物对比表明,上二叠长兴组烃源岩是主要来源,飞仙关组、下志留统烃源岩亦有贡献;催化加氢产物饱和烃及其正构烷烃单体碳同位素组成显示,坡2井飞仙关组储层固体沥青与罐5井飞仙关组烃源岩具有明显的亲缘关系,这也可作为飞仙关组海槽相烃源岩对飞仙关组气藏有贡献的佐证。     

Waxes and asphaltenes in crude oils

High molecular weight (HMW) hydrocarbons (>C₄₀) and asphaltenes are important constituents of petroleum and can cause problems related to crystallization and deposition of paraffin waxes during production and transportation as well as in the formation of tar mats. However, traditional methods to isolate asphaltene fractions, by adding 40 volumes in excess of low boiling point solvents such as pentane, hexane or heptane, can produce asphaltene fractions which are contaminated with a significant amount of microcrystalline waxes (>C₄₀). The presence of these microcrystalline waxes in the asphaltene fractions has the potential to provide misleading and ambiguous results in modeling and treatment programs. The sub-surface phase behaviour of an asphaltene fraction will be quite different from that of a wax-contaminated asphaltene fraction. Similarly accurate modelling of wax drop-out requires information on pure wax fractions and not asphaltene-dominated fractions. Hence the goal of this paper is to describe a novel method for the preparation of wax-free asphaltene fractions. In addition, this method provides a quantitative subdivision of the wax fraction into pentane soluble and insoluble waxes which, when correlated with physical properties of crude oil such as viscosity, pour point, cloud point, etc., may help explain causes of wax deposition during production, transportation and storage of petroleum.     

Geochemical constraints on mixed source and hydrocarbon filling process in the Yingjisu Sag,Tarim Basin,Xinjiang

The Yingjisu Sag was petroliferous for normal oil, condensate oil, reservoir bitumen and natural gases. Geochemical studies showed that natural gases in the Yingjisu Sag were a gas mixture consisting mainly of Cambrian pyrolysis gas, Jurassic condensate oil in well Yingnan 2 and normal oil in well Tadong 2, reflecting the characteristics of marine-phase gases and oils, while crude oils in well Longkou 1 demonstrated the characteristics of both marine and terrestrial oils, which were derived from lower algae and higher plants. Jurassic oils from wells Longkou 1 and Huayingcan 1 and Cambrian crude oils from well Tadong 2 were derived mainly from Cambrian-Lower Ordovician source rocks. Jurassic and Silurian reservoir bitumens from well Yingnan 2 were biodegradated, suggesting they are of marine and terrestrial origins. The bitumens have similar geochemical characteristics, which are correlated well with Ordovician crude oils from well Tadong 2 and Jurassic condensate oil from well Yingnan 2. Based on the characteristics of tectonic evolution in this area and the analysis of hydrocarbon accumulation, the constraints on the mixed source and hydrocarbon filling process in the Yingjisu Sag were brought forward.     

Secondary hydrocarbon generation potential from heavy oil, oil sand and solid bitumen during the artificial maturation

Secondary hydrocarbon generation potentials from natural bitumen, oil sand and heavy oil, representing different residual oil accumulations, were determined by artificial maturation in a closed pyrolysis system. Simulated results indicate that their thermal behavior and reactivity are similar to those of kerogen, and that they can generate hydrocarbons once subjected to suitable geological processes. Overall differences in oil and gas generation potentials among the samples result from differences in the chemical structure of precursor components, physical compaction status, and mineral matrices. Hydrogen rich precursors, such as oil sand and heavy oil, have greater potential to generate hydrocarbons than hydrogen poor ones. Naturally compacted oil sand has slightly higher conversion efficiency than artificially compacted heavy oil as indicated by lower residual bitumen content. However, total gas and liquid oil recovery from oil sand is lower than from heavy oil due to the poor release of pyrolytic products from well compacted and cemented networks in the experiments. Mineral matrices of previous oil deposits also affect further hydrocarbon generation potential. Carbonate matrices inhibit total oil and gas generation, which consequently retains high gas potential at the postmature stage. Traditional oil generation models mainly consider the thermal alteration of kerogen; this study provides supplemental information for superimposed basins where previous oil accumulations may have been destroyed and reburied to serve as secondary sources of oil and gas. Consideration of previous oil residues as potential source rock allows better estimates of available oil resources and the risks associated with their exploration.     

海相油气成藏定年技术及其对元坝气田长兴组天然气成藏年代的反演

我国海相叠合盆地的油气特征及成藏过程表现出很强的复杂性,确定油气成藏年代极其困难,建立有效的成藏定年技术显得尤为迫切.为此基于稀有气体He年代积累效应和油气藏保存机制,建立了油气藏4He成藏定年地质模型及年龄估算公式,明确其为油气成藏定型时间;基于天然气40Ar/36Ar比值与源岩钾丰度及地质时代的关系,建立了追溯油气源岩时代的Ar同位素估算模型.磷灰石、锆石（U-Th）/He定年体系的封闭温度与含油气盆地生油气窗的温度范围较为一致,磷灰石、锆石（U-Th）/He年龄可以揭示含油气盆地抬升剥蚀时间、由构造抬升导致的油气藏调整时间,建立了固体沥青、原油中沥青质提取、溶样、Re-Os纯化富集及分离等Re-Os同位素测年前处理技术,可以直接确定固体沥青、原油等的形成时间.按照含油气系统成藏地质要素形成时间或发生时间先后顺序,提出了从确定源岩形成-油气生成-运移充注-调整改造-成藏定型等成藏过程的定年技术序列.开展四川盆地元坝气田源岩时代、生排烃、运移充注、调整改造及成藏定型等关键过程的时间节点综合研究,明确了元坝气田的主力气源为上二叠统龙潭组烃源岩,两期原油充注时间分别为220~175 Ma、168~140 Ma;油裂解气发生在140~118 Ma,元坝地区约97 Ma以来发生构造抬升,尤其15 Ma以来气-水界面发生调整,约在12~8 Ma气藏最终定型并形成现今的气藏格局.      

四川盆地元坝气田长兴组古油藏的定量恢复及油源分析

目前虽认为元坝气田长兴组天然气主要为原油裂解气,但尚未进行该气田的古油藏的定量恢复并计算原油裂解气的资源量,并系统分析古油藏原油的来源.长兴组储层普遍可见固体沥青,是原油裂解的直接产物,且原油裂解在本区构造抬升变形前就已经完成,因此储层沥青可用来识别古油层的分布.根据储层沥青的纵向和平面分布,确定了7个可靠的古油藏和4个可能的古油藏,并运用容积法恢复出本区聚集的古原油为6.14×108 t,计算出相应的原油裂解气为3 807.08×108 m3,远大于现今气田的天然气探明储量,表明原油裂解气可以提供充足的气源,进一步证明了天然气主要为原油裂解气.通过长兴组储层沥青与不同层系烃源岩干酪根的碳同位素δ13C值对比,并结合烃源层分布和TOC等资料,确定古油藏原油主要来源于有机质类型以Ⅱ型为主的上二叠统吴家坪组烃源岩,其次为长兴组/大隆组烃源岩.后者主要分布在广元-南江-通江地区,该区的天然气勘探不能忽视该套烃源岩的生烃潜力与成藏贡献.      

桂中坳陷海相地层油气成藏与热作用改造

桂中坳陷是在加里东运动基础上形成的晚古生代海相大型沉积坳陷,已演化成为由上古生界和三叠系充填的残留盆地,其中泥盆系深埋地腹,是主要的勘探目的层系。桂中1井揭示泥盆系—石炭系具有两套生储盖组合,钻遇了气测异常、油迹砂岩、固体沥青等三类油气显示,其中泥盆系沥青显示井段累计709m。桂中坳陷古油藏(沥青)主要来源于中—下泥盆统塘丁组和罗富组泥岩。桂中1井和南丹大厂储层固体沥青为运移/成藏的油气发生热裂解而形成的焦沥青。桂中1井经历了两期油气充注,第一期为印支期前的主力生烃期,第二期(晚期)为燕山期—喜马拉雅期,以紧邻油气显示层的可溶烃类为代表。经历了三期油气改造:第一期为印支期前的油气藏经历了地层沉降增温的热裂解作用而演化为固体沥青和甲烷天然气,第二期为燕山晚期岩浆活动导致的更高温度的热蚀变作用,第三期为喜马拉雅期构造抬升的改造或破坏作用对上泥盆统油气藏的影响。晚期成藏的天然气应是下一步的勘探方向。桂中坳陷西部地层保存相对完整(目的层深埋),断裂和岩浆活动相对不发育,可能更有利于天然气的聚集和保存。     

实验室条件下微生物降解原油的地球化学特征研究

通过对胜利油田四个正常原油样品微生物作用前后的族组分及饱和烃色谱质谱分析,发现实验室条件下微生物对原油有明显的降解作用。微生物作用以后的原油族组分其饱和烃相对含量降低,饱/芳比也明显降低,而芳烃、非烃和沥青质的相对含量都不同程度的升高。通过饱和烃色谱-质谱分析,发现微生物作用以后原油正构烷烃被严重降解,姥/植(Pr/Ph)比值和∑C_21-/∑C₂₂₊比值都明显降低。微生物作用原油后能产生表面活性剂,造成了培养基表面张力的降低。