Interaction of copper with fatty acids in Soxhlet extraction and its influence

Treatment with metallic copper for the removal of elemental sulfur from bitumen extracted from sedimentary rocks or petroleum is the most widely used method. Little attention has been paid, however, to its disadvantages. It was observed that copper can interact with some polar organic substances during conventional sulfur removal, which can strongly influence the quantitative and qualitative determination of bitumen, as has been confirmed by interaction of long-chain fatty acids with copper. The copper soap generated was analyzed by element analysis, inductively coupled plasma optical emission spectrometry （ICP-OES）, thermal analysis （TG-DSC） and Fourier Transform Infrared spectroscopy （FFIR）. Mechanism of the interaction was investigated and elucidated. Our experimental results would necessitate improvement of the present method for sulfur removal and/or a search for a new one.     

中国侏罗系煤成油若干问题

在阐述了煤成油的概念，总结和评述了煤生油显微组分，生油门限，生油范围和生油高峰等问题后，本文通过吐哈等盆地侏罗系煤生油显微组分组成特征，可溶有机质演化，成熟度和有机质丰度，油源及原油成熟度对比；含煤岩系中煤层和泥岩的厚度及总量和煤及泥岩最高沥青和总烃转化率的对比； 其族组成和煤成原油的族组成特征的对比，提出了中国侏罗系煤成油盆地中泥岩比煤层对煤成油田形成有大的贡献看法。     

Phenanthrene biomarkers in the organic matter of Precambrian and Phanerozoic deposits and in the oils of the Siberian Platform

The composition and distribution of phenanthrenes (polyaromatic compounds) have been studied in chloroform extracts from dispersed organic matter (OM) of clayey, siliceous, carbonate, and terrigenous rocks of different ages and facies and from some oils of the Siberian Platform. Phenanthrenes have been analyzed by gas chromatography-mass spectrometry. High contents of 1,7,8-trimethylphenanthrene and 1,1,7,8-tetramethyl-1,2,3,4-tetrahydrophenanthrene are present in the OM of Vendian and Cambrian carbonate-shale deposits and in ancient oils of the Nepa-Botuobiya and Anabar anteclises. The OM of Permian continental deposits and oils of the Vilyui syneclise is dominated by 1-methyl-7-isopropylphenanthrene (retene). A triangular diagram for identification of the types of original OM of rocks and classification of genetically related oils has been constructed based on the assessment of phenanthrene biomarker distribution. Putative pathways of the formation of phenanthrene biomarkers are discussed.     

黄骅坳陷古生界潜山储层沥青成因判识

正黄骅坳陷古生界潜山是大港油田重要的油气勘探领域,近年来,先后在王官屯、乌马营潜山古生界发现油气流,且均为石炭—二叠系煤系源岩供烃成藏,如王官屯潜山王古1井二叠系石盒子组发现天然气,同位素特征判断为煤成天然气。这些发现拓展了古生界潜山的勘探领域,表明了石炭—二叠系煤系烃源岩的油气充注范围不仅仅局限于奥陶系碳酸盐岩储层,石炭—二叠系的碎屑岩储层也可以充注成藏,证实了古生界潜山具有更大的油气勘探价值。随着勘探进程与理论认识的不断深化,     

Thermal depolymerization of kerogen and formation of immature oil

Two Chinese immature oil shales from the continental deposits of kerogen type I and II have been thermally treated combined with the technique of supercritical fluid extraction at 630–650 K and 15–25 MPa in a semi-continuous laboratory scale apparatus. Toluence is selected as the solvent. Up to 70–80% of the kerogen matrix can be converted to a thermal bitumen and extracted simultaneously. The chemical structural parameters from the NMR, IR, XRD, ESR and EA analyses of the kerogen and the thermal bitumen show striking resemblance in nature. It implies that the thermal bitumen is primarily a depolymerized product of the kerogen. Based on the GC/MS spectra of the aliphatic eluate of the thermal bitumen, the predominance of the odd/even ratio of the alkanes and the epimeric ratios, such as 20S(20S + 20R) of C-29 steranes and 22S/(22S + 22R) of C-32 terpanes, show that the maturity of the thermal bitumen from these oil shales is comparable to that of commercial immature oils from East China. The thermal bitumen is thought to be an intermediate product of the thermal degradation of kerogen.Since the thermal bitumen is mainly composed of asphaltenes and resins, it has a structure of gel. The gel-state bitumen may turn to sol-state readily due to its low aromaticity and polarity, or due to selective adsorption of asphaltenes by clay minerals. Then the migration potential of the bitumen is enhanced.Consequently, under favorable geological conditions, the thermal depolymerization of kerogen seems to be a probable mechanism to explain the formation of immature oils.     

Anomalous Enrichment of Silver in Organic Matter of the Songxi Shale-hosted Ag-Sb Deposit in Northeastern Guangdong

The silver contents of organic matter in the host rocks of the Songxi shale-hosted Ag-Sb deposit of northeastern Guangdong, South China, have been directly determined using the electron microprobe technique. The silver contents in two types of organic matter, marine vitrinite and solid bitumen, vary in the range from 100×10-6to 350×10-6, which are from tens of times to thousands of times higher than those of the host rocks in the ore deposit. The average silver content of the organic matter is also several times higher than the pay grade of silver for commercial mining of the ore deposit. It is quite obvious that the organic matter of the host rocks in the ore district is characterized by an anomalous enrichment of silver. The results of this study indicate that the silver anomalies in the organic matter have been derived from both the host rocks and the silver-bearing fluids of the Songxi black shale ore source. In the course of sedimentation and later hydrothermal reworking, organic matter was able     

Lower palaeozoic and precambrian petroleum source rocks and the coalification path of alginite

Organic-rich samples derived from a Middle Cambrian Formation in the Georgina Basin, and from the Middle Proterozoic of the McArthur Basin in northern and central Australia, yielded alginite ranging from immature oil shale material to overmature residue. A maturation scale has been developed based on the thermal evolution of alginite as determined from reflectance and fluorescence. The coalification path of alginite is marked by jumps in contrast to the linear path of wood-derived vitrinite. Six zones have been recognised, ranging from undermature (zone I), through the mature (zones II/III), followed by a stable stage of no change (zone IV) to the overmature (zones V and VI). The onset of oil generation in alginite as evident from the present study is at 0.3% R_{o Alg.} and is expressed in a change of fluorescence from yellow to brown, and a coalification jump from 0.3 to 0.6% R_o of Alg. In many boreholes zone III can be distinguished between 0.6 and 0.8% R_o of Alg. where subsequent oil generation occurs. Zones II and III represent the oil window.A zone of little or no change designated zone IV, at of alginite follows zones II/III. A marked coalification jump characterises zone V, where a pronounced change in reflectance occurs to >1.0% R_{o Alg.}, signifying peak gas generation. The border of oil preservation lies at the transition of zone V and VI, at 1.6% R_{o Alg.} In zone VI gas generation only occurs.Comparison of reflectance results with experimental and geochemical pyrolysis data supports high activation energies for hydrocarbon generation from alginite, and therefore a later onset of oil generation than other liptinite macerals (i.e. cutinite, exinite, resinite) as well as a narrow oil window.Transmission electron microscopy (TEM) confirms that alginite does not go through a distinct intermediate stage but that the percentage of unreacted organic matter decreases as maturation proceeds. A clear distinction can be made in TEM between immature alginite, alginite after oil generation, and alginite residue following gas generation. Alginite beyond 1.6% R_o acquires very high densities and the appearance of inertinite in TEM.Bitumens/pyrobitumens make a pronounced contribution to the organic matter throughout the basins and have been shown to effect pyrolysis results by suppressing T_max. The bitumens/pyrobitumens have been divided into four groups, based on their reflectance and morphology, which in turn appears to be an expression of their genetic history. Their significance is in aiding the understanding of the basins' thermal history, and the timing of oil and gas generation.     

鄂尔多斯盆地能源矿产氯仿沥青Sm-Nd同位素研究

对鄂尔多斯盆地石油、煤、含铀砂岩及其围岩的氯仿沥青进行了Sm-Nd同位素研究。结果表明,盆地流体(包括深部流体)活动具有多期性,且后期的流体活动对铀矿床的形成具有重要作用;赋存于同一套地层中的含铀砂岩沥青、煤沥青及石油沥青,虽然均具有富集地幔特征,但并非同期活动的产物;东胜矿区侏罗系直罗组煤沥青和盆地西南部陈家山矿区侏罗系延安组的煤沥青,源区时代上存在较大差异,伴生沥青并非全部由煤的热演化形成,可能还存在外来流体的加入,且东胜直罗组煤的伴生沥青较延安组煤的伴生沥青来源深度更大;盆地内马岭油田的直罗组石油沥青、陈家山延安组煤层石油沥青及其煤沥青在源区特征上具有内在联系。     

中国南方存在印支期的油气藏——Re-Os同位素体系的制约

利用Re-Os同位素方法开展富含有机质的沥青、原油等的研究,是确定油气成藏时间和破坏时间有效的但极富挑战性的新途径,在国内尚无研究实例报道。以我国南方最大的古油藏之一的麻江古油藏中的沥青为主要对象,采用Re-Os同位素方法试图限定油气的成藏时间和破坏时间。研究表明,麻江古油藏的固体沥青Re、Os同位素质量分数分别在41.5×10-6～642×10-6和0.21×10-6～12.15×10-6之间,N(187Re)/N(188Os)比值较高,且变化范围较大,在270.90～4074.99之间,Os同位素组成指示中等放射成因,其N(187Os)/N(188Os)比值在0.3400～3.6557之间变化。所有沥青样品的模式年龄在28～144Ma之间变化,集中在85Ma左右。通过沥青Re-Os同位素研究,结合详细地质资料,认为麻江古油藏的成藏时间为印支期—早燕山期(144Ma之前),而油藏破坏时间为燕山晚期即85Ma左右。     

麻江古油藏油源识别与油气运聚分析：来自油气地球化学的证据

充分考虑热演化过程中烃源岩干酪根、族组分、固体沥青及正构烷烃碳同位素相互关系及变化规律,通过地球化学分析并结合前人碳同位素及芳烃标志物研究进行综合分析,结果表明古油藏各区域储层早期均存在下寒武统黑色泥岩来源,后期来源有较大差别,麻江古背斜以南各地沥青均不同程度与中寒武统都柳江组有关,北凯里液态原油及油苗为五峰组及龙马溪组印支期成藏产物,其保存环境为储层早期成岩过程中形成的独立封闭系统。在油源识别的基础上,结合构造地质背景、油气成藏条件及流体活动规律分析,认为黔南坳陷及邻区下寒武统、都柳江组、五峰组及龙马溪组烃源岩的分布控制了该区油气富集规律,黔南海西期断裂系统与加里东运动形成的不整合面构成不同期次油气运聚的输导系统,海西期形成的一系列正断裂是麻江古油藏成藏的关键。