在索氏抽提过程中铜与有机物的反应

将黄县褐煤、鄂尔多斯盆地神山褐煤、塔里木盆地泥质灰岩、柴达木盆地灰质泥岩分为A、B2个系列.利用索氏抽提法对以上样品进行对比抽提实验:A系列抽提过程中加铜脱硫,B系列抽提过程中不加铜.实验结果表明:用来脱硫的铜可与抽提物中的某些有机质发生反应,生成有机金属化合物,而大大影响了样品前处理的结果.如果在抽提过程中先不加入铜,待抽提结束后运用柱色谱法将饱和烃和硫作为一个馏分从抽提物中分离出来,然后再进行脱硫,这样就可以很大程度上降低铜对有机质定量测定的影响.     

从有机质成熟度看四川盆地下古生界油气勘探

从回顾有机质成熟度检测研究现状入手，论证认为镜质体反射率至今仍是有机质成熟度研究的最佳参数。以此为据，编绘了四川盆地上二叠统有机质成熟度图；通过对其与下伏产层油气属性关系的分析，探讨了四川盆地下古生界因缺乏镜质体作为检测对象而被迫选用其他参数用于有机质成熟度划分所存在的可变因素；最后借用四川盆地上二叠统有机质成熟度演变趋势分析结果，确认川东-川东北有机质过成熟地区的高陡构造仍不失为该区天然气勘探的目标区。     

THE ORGANIC MATTER IN OIL SHALES FROM THE LOWMEAD BASIN, QUEENSLAND, AUSTRALIA

Oil shales contain organic matter from many sources, deposited under a variety of environmental conditions, which influence the potential for their commercial exploitation. Variations in organic matter type within the oil shales of the Lowmead Basin have been identified with reference to an integrated physico-chemical classification. The pyrolytic yield of the oil shales has been shown to correlate better with this classification than with a purely chemical classification. While the pyrolytic yield, in litres per metric tonne (l/mt), is satisfactory as a commercial assessment of the oil shales, the addition ofTOC data is an additional indicator of the potential quantity and quality of the shale oil.     

LOWER CARBONIFEROUS SHALES IN THE EASTERN TAURIDE BELT,SOUTHERN TURKEY: SOURCE ROCK CHARACTERISTICS

Lower Carboniferous (Tournaisian‐Visean) shales, sandstones and limestones are exposed at the surface in autochthonous units in the Eastern Taurides, southern Turkey. This study investigates the organic geochemical characteristics, thermal maturity and depositional environments of shale samples from two outcrop locations in this area (Belen and Naltas). The total organic carbon (TOC) contents range from 0.11 to 5.61 wt % for the Belen samples and 0.04 to 1.74 wt % for the Naltas samples. T_max values ranging from 432–467 °C indicate that the samples are in the oil generation window T_max and are thermally mature. Rock‐Eval pyrolysis data indicate that the organic matter in the shales is composed mainly of Type II and III kerogen. Solvent extract analyses of the samples show a unimodal n‐alkane distribution with a predominance of low carbon number (C₁₃‐C₂₀) n‐alkanes. Pr/Ph ratios and CPI values range from 1.57–1.66 and 1.08–1.11, respectively Pr/n‐C₁₇ and Ph/n‐C₁₈ ratios also indicate that the shales consist of mixed Type II/III organic matter. Sterane distributions are C₂₇>C₂₉>C₂₈ as determined by the sum of normal and isosteranes, suggesting marine depositional conditions 20S/(20S+20R) and ββ (ββ+αα) C₂₉ sterane ratios range from 0.51–0.54 and 0.53–0.57, respectively. These values are high and 20S/(20S+20R) sterane isomerisation has reached equilibrium values. Tricyclic terpanes are abundant on m/z 191 mass chromatograms and C₂₃ tricyclic terpanes are the dominant peak, which indicates a marine depositional setting. C₂₉ norhopane has a higher concentration than C₃₀ hopane, and C₃₀ diahopane and C₂₉Ts are present in all the samples. Ts and Tm were recorded in similar abundances. Moretane/hopane ratios are very low. 22S homohopanes are dominant over 22R homohopanes, and the C₃₂ 22S/(22R + 22S) C₃₂ homohopane ratios are between 0.58 and 0.59, indicating that homohopane isomerisation has reached equilibrium. C₃₁ homohopanes are dominant and the abundance of homohopanes decreases towards higher numbers. Although regional variations in the level of thermal maturity of Upper Palaeozoic sediments throughout the Taurus Belt region largely depend on burial depth, organic geochemical data indicate that the Lower Carboniferous shales in the eastern Taurus region (Naltas and Belen locations) have potential to generate hydrocarbons. These shales are thermally mature and have entered the oil generation window.     

ORGANIC GEOCHEMISTRY OF THE GÖYNÜK AND SEYITOMER OIL SHALES OF TURKEY

The GCöynük and Seyitomer oil shales overlie coal seams. An investigation of their geochemistry by solid-state and high-resolution nuclear magnetic resonance, infra-red spectroscopy and gas chromatography/mass spectrometry of the extracted bitumen suggests a classification as immature Type I kerogens. However. the n-alkane distribution is consistent with a substantial input from terrestrial plants .     

ORGANIC GEOCHEMISTRY OF THE GÖYNÜK AND SEYITOMER OIL SHALES OF TURKEY

The Göynük and Seyitomer oil shales overlie coal seams. An investigation of their geochemistry by solid-state and high-resolution nuclear magnetic resonance, infra-red spectroscopy and gas chromatography/mass spectrometry of the extracted bitumen suggests a classification as immature Type I kerogens. However, the n-alkane distribution is consistent with a substantial input from terrestrial plants.     

江汉盆地下第三系烃源岩有机岩石学研究

作者采用有机岩石学全岩分析技术,系统研究了江汉盆地下第三系烃源岩的显微组分组成、生烃组分及有机质热演化。江汉盆地烃源岩形态显微组分含量明显偏低,平均仅占全岩体积的1.5%。显微组分组成中富含腐泥组,相对发育镜质组和壳质组,贫惰性组。有机质类型多为Ⅱ、Ⅰ型。藻类体、矿物沥青基质是该区主要生烃组分。文中利用镜质体反射率R_o及富氢组分和非烃馏分的荧光参数探讨了江汉盆地烃源岩有机质演化特征,提出了有机质的热演化阶段的划分方案。     

ORGANIC MATTER AS INDICATOR OF THE DEGREE OF METAMORPHISM OF THE CARBONIFEROUS ROCKS IN THE SOUTH WALES COALFIELDS

Isoreflectance maps of vitrinites in coals and phytoclasts (coaly inclusions) in the Coal Measures of S. Wales show a progressive increase in vitrinite reflectance with increase in coal rank and grade of metamorphism towards the anthracite area in the west, without significant variation in reflectances of coals with present depth. Differences between values of vitrinite reflectance in coals and phytoclasts in the same profile are recorded and attributed to variations in depositional environments, and to susceptibility to alteration of the host rocks. Spores in the Coal Measures are progressively carbonized (from golden brown to black) towards the west, and this is not a function of present depth of burial. Reflectance of vitrinites in coals, degree of spore carbonization and coal rank are used in definition of three different diagenetic zones in the coalfield. The Coal Measures could have acted as a source for accumulations of gas in the Permo-Triassic sequence of the south Irish Sea, if necessary geologic conditions are present. Burial metamorphism (application of Hilt's law) could have caused the coalification of S. Wales coals up to the high and medium volatile bituminous stages (up to the late diagenetic stage). A relationship is established between the lateral variation in coal rank in the coalfield and the regional variation in coal rank in the southern British Isles, where two regions of markedly different geothermal history are recognised. The Diagenetic Zone in the E and S parts of the coalfields marks the final stage in the thermal history of the cold region (the W margin of London Stable Massif), whilst the Anchimetamorphic Zone in the NW part (the anthracite area) represents the final stage in the thermal history of the hot region (the S margin of St. George's Land).
Phytoclasts and spores are recorded for the first time from the Dinantian massive limestones of S. Wales.     

上元古界下马岭组页岩干酪根的油气生成模拟实验

本模拟实验主要对华北上元古界下马岭组页岩干酪根的热演化特征和规律进行研究。实验研究表明,上元古界下马岭组有机质具有某些新的热演化特征;同时,作者根据实验结果,建立了中、上元古界油气生成演化模式,并确定了成熟度的指标界限,为中、上元古界有机质成熟度的划分和油气资源的评价提供了依据。      

下古生界烃源岩有机显微组分分类与应用

运用全岩光片、干酪根光片、干酪根薄片和光薄片等手段,对塔里木盆地下古生界烃源岩有机显微组分进行观察研究,对各种组分进行特征描述,根据显微组分的成因及光性特征,将其分为原生形态有机质、原生无形态有机质及次生有机质3类,并在此基础上确定了下古生界烃源岩有机显微组分的加权系数。应用该方案对塔里木盆地孔雀河1井O_2+3q烃源岩有机质类型进行分析,6个样品中有1个为Ⅰ型,3个为Ⅱ₁型,2个为Ⅱ₂型。     

渤海湾盆地黄骅坳陷下古生界碳酸盐岩有机地球化学特征

对渤海湾盆地黄骅坳陷下古生界碳酸盐岩样品开展了有机地球化学研究,研究揭示氯仿沥青A中正构烷烃的碳数分布以单峰型为主(主峰碳为nC₁₆或nC₁₈),奇偶优势值接近于1.0,升藿烷成熟度参数为0.58~0.63,显示其处于高成熟演化状态;Pr/Ph值普遍接近于1或略大于1,反映了一种弱还原─弱氧化的沉积环境.氯仿沥青C中正构烷烃碳数分布主要为双峰型,反映其成熟度低于氯仿沥青A;Pr/Ph值均接近于1,反映了弱还原─弱氧化的沉积环境.多数样品的氯仿沥青A和氯仿沥青C具有相似的碳同位素组成分布模式,反映氯仿沥青C中正构烷烃碳同位素组成并没有受到成岩后地质作用的强烈影响,保存了早期有机质的特征,因而可用于恢复古沉积环境,为环渤海地区下古生界潜在原生油气藏的判识提供依据.     

URANIUM SPECTRAL GAMMA-RAY RESPONSE AS A PROXY FOR ORGANIC RICHNESS IN BLACK SHALES: APPLICABILITY AND LIMITATIONS

In many organic-rich, low-carbonate hemipelagic shales, there is a stable and close correlation between the uranium and TOC contents. In this paper, we present a number of case studies using our own data and that from previous publications to investigate black shales with (1) good, (2) fair-to-good and (3) poor U/TOC correlations. U/TOC ratios in the different black shale units are compared to each other, and possible reasons for the observed variations are discussed.
In general, the U/TOC ratio in a black shale is controlled by a number of factors which include for example the primary uranium content of the water body, the carbonate content and the sedimentation rate. The development of a stable U/TOC ratio may be inhibited by the presence of phosphate, by a high carbonate or sand content, by dissolution ("burn-down") of uranium during intermittent oxic periods, and by large-scale diagenetic remobilisation of uranium. In suitable black shale systems, vertical variations in organic richness can be approximated by measuring the uranium content using spectral gamma-ray measurements. This may be especially important in outcrop studies because gamma-ray logging is a straightforward field technique. Before the uranium content can be used as a proxy for TOC content in a black shale system, however, a thorough calibration of uranium and TOC is necessary, in order to determine the stratigraphic and regional limits of the derived U/TOC ratios and to establish the presence of a stable U/TOC correlation.     

有机相在油气源岩与油气评价中的作用——以下扬子区二叠系为例

本文根据沉积相、沉积物源、生物组合、地球化学相、有机质丰度和类型、生烃潜力等特征对下扬子区二叠系的主要油气源岩有机相进行综合研究,同时阐明有机相的概念,提出有机相的划分依据和指标界限,将有机相分为强油相(A)、油相(B₁)、油裂解气相(B₂)、油气混合相(B-C)、无油气相(D).      

周口盆地白垩纪油源岩孢粉化石颜色及其有机质类型

周口盆地位于河南东部,下白垩系在井下很发育。本文采用钻孔中的一些岩心,经过在显微镜下观察孢粉化石和有机质碎片。根据孢粉化石颜色的变化,将其有机质成熟度的标准,划分为四个阶段,即:未成熟阶段、成熟阶段、高成熟阶段、过成熟阶段。根据孢粉化石颜色特征,周口盆地的生油门限在1900米左右,在井深4000米时有机质材料已达到高成熟阶段,作者认为在这些地区,在井深1900—4000米有好的生油潜力。     

THE NATURE AND PRESERVATION OF ORGANIC MATTER IN HOLOCENE LACUSTRINE/DELTAIC SEDIMENTS OF LOWER MESOPOTAMIA, SE IRAQ

Organic-geochemical studies of sediments at the surface and in shallow boreholes in the Tigris-Euphrates Delta of SE Iraq are integrated in this paper with sedimentological and stratigraphic studies. Limited organic preservation was found to have occurred in surface sediments from marshland areas ("Ahwar"), although organic-rich sediments were observed within older Holocene borehole sequences.
Reeds of Phragmites and Typha sp. are the main source of organic material in both the surface and the underlying sediments in this area. Petrographic studies indicated that this material consists mainly of "immature" components such as woody structures, algal amorphous and herbaceous matter, with some marine structures and pollen.
The principal factor controlling organic-matter preservation in this arid deltaic setting seems to have been the comparatively high rate of sedimentation, particularly in the early-middle Holocene. Most of these organic-rich sediments (5–15% TOC) are overlain by middle Holocene brackish/marine sediments of the transgressive Hammar Formation. The organic-rich sediments are generally older than these transgressive sediments (i.e. 6,000–9,000 years BP, according to their location within the study area).     

SOURCE ROCK POTENTIAL OF THE UPPER JURASSIC – LOWER CRETACEOUS SUCCESSION IN THE SOUTHERN MESOPOTAMIAN BASIN,SOUTHERN IRAQ

This paper reports on the hydrocarbon potential of subsurface samples from the Upper Jurassic Lower Cretaceous succession at the Rumaila (North and South), Zubair, Subba and West Qurna oilfields in southern Iraq. A total of 37 fine‐grained core samples of the Sulaiy, Yamama, Ratawi and Zubair Formations from ten wells were analyzed. Contents of organic carbon and sulphur were measured; other analyses included Rock‐Eval pyrolysis, optical microscopy in incident light, solvent extraction and gas chromatography of non‐aromatic hydrocarbons. The results indicated that the samples from the Cretaceous succession (Yamama, Zubair and Ratawi Formations) are at moderate levels of thermal maturity, whereas samples from the Upper Jurassic – Lower Cretaceous Sulaiy Formation are at a stage of thermal maturity beyond peak oil generation. According to the results of this study, the Sulaiy Formation is an excellent highly‐mature source rock and it is probably responsible for the generation of large quantities of oil in the study area. The samples differ with respect to their organic fades and biomarker distribution, indicating that palaeo depositional conditions varied significantly.     

粘土膜对砂岩储集性能的影响——以塔里木盆地群6井区泥盆系东河塘组下段为例

通过对岩石的铸体薄片、扫描电镜、压汞及物性等资料分析认为:塔里木盆地群6井区泥盆系东河塘组下段砂岩中粘土矿物薄膜的成因可分为原生式和自生式,其中以自生式为主。粘土矿物薄膜的形成期往往在成岩早期(或同生成岩期),粘土膜的发育与面孔率基本成正相关关系,与储层孔隙结构成负相关关系。东河塘组下段粘土膜发育的储层(泥质含量0.5%~3%)孔隙度一般为7%~17.6%,平均为11.53%,渗透率一般为(0.1~10)×10-3μm2,平均为4.15×10-3μm2;明显高于东河塘组上段粘土膜不发育储层物性,其孔隙度平均为5.23%,渗透率平均为2.88×10-3μm2。粘土膜与储层沉积相带、储层温压系统及早期油气注入较为密切,一般在临滨相带的下临滨—中临滨微相中较为常见,而在泥质淘洗相对干净的上临滨—前滨微相中难以保存,成岩早期油气的注入及异常高压封存体系(群6井区压力系数为1.59)的存在对粘土膜的保存完好起到决定性作用。      

MILD HYDROCRACKING — A STATE OF THE ART

This paper is a brief, but not exhaustive review of the literature of the catalytic mild hydrocracking processes. It includes data characterizing reactivities, reaction network and kinetics of mild hydrocracking reactions. This review is designed for use as a reference for further research and development work in the field of mild hydrocracking.