中扬子地区下古生界页岩气的勘探潜力

页岩气有别于已经大量开采的常规天然气,在成藏机理和赋存特征方面都有其独特的特点,识别与评价页岩气的方法也有别于以往对常规天然气气藏的评价模式。泥页岩厚度、埋深、总有机碳含量、成熟度是其重要的判别指标。对比美国东部典型页岩气产出地区页岩气藏地质条件,湘鄂西的恩施—建始、桑植—石门地区为下寒武统、志留系页岩气勘探有利地区。     

中扬子地区下古生界页岩气的勘探潜力

页岩气有别于已经大量开采的常规天然气,在成藏机理和赋存特征方面都有其独特的特点,识别与评价页岩气的方法也有别于以往对常规天然气气藏的评价模式.泥页岩厚度、埋深、总有机碳含量、成熟度是其重要的判别指标.对比美国东部典型页岩气产出地区页岩气藏地质条件,湘鄂西的恩施一建始、桑植一石门地区为下寒武统、志留系页岩气勘探有利地区.     

中扬子地区下古生界页岩气的勘探潜力

页岩气有别于已经大量开采的常规天然气,在成藏机理和赋存特征方面都有其独特的特点,识别与评价页岩气的方法也有别于以往对常规天然气气藏的评价模式。泥页岩厚度、埋深、总有机碳含量、成熟度是其重要的判别指标。对比美国东部典型页岩气产出地区页岩气藏地质条件,湘鄂西的恩施—建始、桑植—石门地区为下寒武统、志留系页岩气勘探有利地区。     

Weathering characteristics of the Lower Paleozoic black shale in northwestern Guizhou Province,south China

The northwestern Guizhou in the Yangtze Craton of south China has a tremendous potential of shale gas resource. In this paper, we present results from major and trace elements, total organic carbon, mineralogical composition analysis and petrophysical parameters to characterise shale weathering features. Further, the differences of black shale between underground and outcrops have also been presented to examine the changes of black shale after weathering. Our results show that the trace elements of shale have varying degrees of loss in the weathering leaching process, both in Niutitang shale and Longmaxi shale, the loss of B, V, Ni, Cu, Zn and Ba is obvious, but the element migration quantity in the former is greater than in the latter. Decomposition of minerals such as pyrite, feldspar and calcite result in the leaching of Na, Ca, Mg and Fe. The loss rate of total organic carbon (TOC) in black shales ranges from 18% to 70% with an average of 43%; moreover, the loss of organic carbon in samples with high TOC content is larger than in those samples with low TOC content. Results following the testing of porosity and permeability show that porosity increases significantly after weathering but permeability changes little. Furthermore, the increment of porosity is greater in the Niutitang shale (with more sulphide minerals) than in the Longmaxi shale, suggesting that the oxidation of sulphide minerals may have led to the formation of an acidic environment, causing the other minerals in the black shale to weather more quickly, thus resulting in increased porosity. The content of clay minerals in the core samples is slightly lesser than the outcrop samples, but the TOC content in the core samples is greater and has a larger specific surface area. This suggest that the TOC content played a decisive role on the specific surface area of shale. In addition, changes in the black shale caused by the weathering process mainly depend on the mineral composition and the TOC content in shale. In this study, we try to establish relations between outcrop samples and core samples, in order to better understand the underground characteristics of shale reservoir.     

黔西北地区龙马溪组页岩气储层孔隙特征及其储气意义

中国南方下志留统龙马溪组海相页岩有机质含量高且热成熟度高,是重要的页岩气储集层位。本文以黔西北地区习页1井与桐页1井的岩心样品为研究对象,研究龙马溪组页岩的孔隙特征及孔隙发育的影响因素,并对其储气性能进行综合的分析与评价。通过扫描电镜的大量观察可知,该区龙马溪组页岩内发育的孔隙多为纳米(nm)量级,包含矿物基质孔(可分为粒间孔和粒内孔)、有机质孔以及微裂缝等多种类型的孔隙,其中有机质孔最为发育。通过测试可知,该区页岩的总有机碳(TOC)含量平均为3.80%,热成熟度(Ro)平均为2.73%,有效孔隙度平均为1.56%;主要组成矿物为黏土矿物与碎屑矿物(石英、长石等),黏土矿物含量平均为32.42%,碎屑矿物含量平均为43.97%;BET比表面积平均为16.98m2/g,BJH总孔体积平均为0.013 7mL/g,孔隙的平均孔径为33.75nm。通过分析可知,TOC含量为孔隙发育的主要影响因素,样品的有效孔隙度与TOC、碎屑矿物含量呈线性正相关关系,与黏土矿物含量呈线性负相关关系。另测得样品对甲烷气体的饱和吸附量平均为2.42m3/t,饱和吸附量与TOC含量呈强烈的正相关性,TOC含量为吸附性能的主控因素;饱和吸附量与有效孔隙度、碎屑矿物含量、BET比表面积以及BJH总孔体积均呈明显的正相关性,而与黏土矿物含量的相关性不显著。     

四川盆地下古生界硅质页岩层系中硅质来源及其对有机质保存的影响初探

四川盆地下古生界两套硅质页岩层系(寒武系底部页岩和奥陶系—志留系五峰组—龙马溪组页岩)是其重要的页岩气产层,五峰组—龙马溪组硅质含量与TOC及含气量呈正相关性,暗示硅质矿物对该地区页岩气的生成具有重要意义。但硅质来源复杂,且存在后期硅质流体的注入。因此,本文在总结前人的研究成果基础上,对四川盆地寒武系底部硅质岩系和五峰组—龙马溪组硅质岩系的硅质特征进行了详细的岩石学分析,揭示了3种硅质来源特征:(1)同沉积无机硅质流体;(2)生物硅;(3)后期无机硅质流体。其中寒武系底部以同沉积无机硅质流体和生物硅来源为主,同沉积硅质流体导致有机质快速石化埋藏,有机质内部结构及形态保存较好;五峰组—龙马溪组硅质来源以后期无机硅质流体和生物硅来源为主,有机质在保存过程中受硅质流体的影响很小,有机质腐泥化作用充分,内部结构和形态多数保存较差。该研究初步揭示了两套页岩层系的硅质发育岩石学特征,及其对有机质保存的影响,期望能为四川盆地两套页岩气储层差异性提供新的思路和基础地质数据。     

四川盆地下古生界硅质页岩层系中硅质来源及其对有机质保存的影响初探

四川盆地下古生界两套硅质页岩层系是其重要的页岩气产层,五峰组—龙马溪组硅质含量与TOC及含气量呈正相关性,暗示硅质矿物对该地区页岩气的生成具有重要意义。但硅质来源复杂,且存在后期硅质流体的注入。因此,本文在总结前人的研究成果基础上,对四川盆地寒武系底部硅质岩系与五峰组—龙马溪组硅质岩系的硅质特征进行了详细的岩石学分析,揭示了3种硅质来源特征：①同沉积无机硅质流体;②生物硅;③后期无机硅质流体。其中寒武系底部以同沉积无机硅质流体与生物硅来源为主,同沉积硅质流体导致有机质快速石化埋藏,有机质内部结构及形态保存较好;五峰组—龙马溪组硅质来源以后期无机硅质流体与生物硅来源为主,有机质在保存过程中受硅质流体的影响很小,有机质腐泥化作用充分,内部结构和形态多数保存较差。该研究初步揭示了两套页岩层系的硅质发育岩石学特征,及其对有机质保存的影响,期望能为四川盆地两套页岩气储层差异性提供新的思路与基础地质数据。     

Investigation of catalytic effects of indigenous minerals in the pyrolysis of Aleksinac oil shale organic matter

The catalytic effect of indigenous minerals in the pyrolysis of Aleksinac (Yugoslavia) oil shale was studied in this paper. The substrates were prepared by gradual removal of the mineral constituents (carbonates, silicates, pyrite) and the free and bound bitumens. The substrates were analyzed by chemical methods, X-ray diffraction, porosimetry, thermal analysis, ¹³C NMR, and standard ASTM Micro Activity Test (MAT) designed for the investigation of cracking catalysts. The liquid pyrolysis products were analyzed by organic geochemical techniques as well. Based on the yields of gaseous and liquid products and the coke, conversion degrees, GC analyses (MAT parameters) and weight losses (TG parameter), the catalytic effect of indigenous mineral components in the pyrolysis of Aleksinac oil shale organic matter was found to be very low. The results suggested that principal organic matter changes should be attributed to thermal rather than to catalytic cracking.     

富有机质海相与陆相页岩的对比研究——以南方早古生代和华北石炭-二叠纪页岩为例

以南方早古生代海相页岩和华北石炭-二叠纪陆相（包括海陆交互相）页岩为研究对象,以场发射扫描电镜微观观测和相关物化测试结果为基础资料,重点对页岩的矿物成因、显微组分、有机质孔隙、岩石力学性质等进行对比性研究。结果表明：海相页岩与陆相页岩有异有同;海相页岩的基本特征是自生矿物多于陆源碎屑,自生石英含量丰富且与有机质同源分异,交互共生,显微组分是以低等生物为原始质料的沥青质体,且纳米级孔隙发育较好;陆相页岩的基本特征是陆源碎屑和泥质为主,自生矿物含量少,显微组分主要是以高等植物为原始质料的各种有机碎屑体,有机质纳米孔隙不发育。这些基本特征导致海相页岩和陆相页岩的生烃潜力、储层物性、岩石可压裂性等均有明显差异,页岩气资源评价与勘探开发需要区别对待。     

Diagenesis of organic matter and fine clay minerals: a comparative study

A geochemical study has been made of fine clay minerals and organic matter in subsurface shale samples from the Canadian Northwest Territories. The mixed layer clays comprise smectite-vermiculite-illite but are transformed during thermal diagenesis to a pseudo-quaternary system (smectitevermiculite-illite-chlorite) by incorporation of amorphous inorganic material. The first clay dehydration occurs prior to hydrocarbon generation and is accompanied by adsorption of K⁺ and substitution of Al³⁺ for Si⁴⁺ in the clay lattice. Vermiculite is an intermediary in the transformation of smectite to illite and in the presence of Ca²⁺ ions delays the second dehydration step to the zone where cracking of liquid hydrocarbons to gas occurs.Hydrocarbon generation commences at a vitrinite reflectance level of ? 0.5% R₀ maximum in both amorphous and woody-herbaceous organic matter but does not reach a significant level in the latter case until reflectance levels of 0.7% R₀ maximum. The pristane to phytane ratio and proportion of n-alkanes and acyclic isoprenoids increase during hydrocarbon generation from woody-herbaceous organic matter. Anomalous hydrocarbon yields from certain samples are attributed to high concentrations of plant resins. Destructions of liquid hydrocarbons by cracking commences at a reflectance level of 1.0% R₀ maximum and is essentially complete by a reflectance level of 1.4% R₀ maximum. The proportion of n-alkanes in the saturates decreases during cracking of the liquid hydrocarbons.     

黔北黄平地区黄地1井下寒武统发现海相页岩气

正1研究目的(Objective)中国南方下寒武统牛蹄塘组广泛发育暗色页岩,有机质含量丰富,沉积厚度大,但普遍存在有机质成熟度过高导致页岩气赋存不利等因素。贵州黄平地区牛蹄塘组为一套深水陆棚相沉积,以炭质页岩为主,具有页岩厚度大、有机质含量高、成熟度适中且构造保存较好等有利条件,目前尚未获得页岩气调查突破。在前期研究的基础上,为摸清牛蹄塘组在该区地层发育,力争获得页岩气发现,在武陵山褶皱带南部贵州黄平地区上塘复背斜东翼南段部署实施了黄地1井,钻遇牛蹄塘组见良好油气     

南方下古生界页岩中有机质赋存状态及其成因

页岩有机质特征是页岩气勘探开发研究的重要内容之一。同时制取页岩的抛光面和自然断面,借助场发射扫描电镜,观测南方多省（市）下古生界页岩有机质的电子图像特征及其赋存状态。从大量样品的观测结果中归纳得出,在抛光面上有机质的赋存状态有条带状、散块状、填隙状、互裹状;在自然断面上有交互状、薄膜状、条带状。这些赋存状态反映出有机质与矿物质的成因关系有同生、胶结和分异。研究结果从微米级-纳米级尺度上为页岩气理论研究和勘探开发提供深层次的直观信息。     

Physical protection of lignin by organic matter and clay minerals from chemical oxidation

The role of organic matter (OM) concentration, structure and composition and how these relate to mineral protection is important for the understanding of long term soil OM dynamics. Various OM–clay complexes were constructed by sequential sorption of lignin and dodecanoic acid to montmorillonite. Humic acid–montmorillonite complexes were prepared at pH 4 and 7 to vary OM conformation prior to sorption. Results obtained with constructed OM–clay complexes were tested with isolated mineral fractions from two soils. Oxidation with an acidic NaClO₂ solution was used to chemically oxidize lignin in the OM–clay complexes, sand-, silt- and clay-size soil fractions to test whether or not it can be protected from chemical attack. Gas chromatography–mass spectrometry was used to analyze lignin-derived phenols, cutin OH–acid (after CuO oxidation), fatty acid and n-alkanol concentrations and composition. We found that carbon content was not solely responsible for lignin stability against chemical oxidation. Lignin was protected from chemical oxidation through coating with dodecanoic acid and sorption of humic acid to clay minerals in a stretched conformation at pH 7. Therefore, interactions between OM constituents as well as OM conformation are important factors that protect lignin from chemical oxidation. Lignin-derived phenol dimers in the Grassland-Forest Transition soil fractions were protected from chemical oxidation to a greater extent compared to those in Grassland soil fractions. Therefore, although lignin was protected from degradation through mineral association, the extent of this protection was also related to OM content and the specific stability of lignin components.     

页岩气储层孔隙类型及特征研究:以渝东南下古生界为例

通过薄片分析、扫描电镜及氩离子抛光技术,对渝东南下古生界含气页岩中的孔隙类型及特征进行了分类观察、描述,结合有机碳含量、X衍射、岩石物性、氮气吸附及甲烷等温吸附实验测试,分析了页岩气储层中各类孔隙的储气贡献,探讨这些孔隙对页岩中烃类运移的影响。研究认为,有机质孔隙、颗粒内孔、粒间孔隙及微裂隙是页岩气储层孔隙的4种类型,有机质表面的分散状孔隙多为nm级,石英碎屑可形成粒内或粒间孔隙,黄铁矿颗粒内部小晶体排列分布产生孔隙空间,黏土絮状沉淀形成片粒状结构孔隙,微裂隙普遍发育在页岩基质中,可达mm级。不同类型的孔隙能够为页岩气的赋存提供不同尺度的储集空间,页岩吸附含气量与表征孔隙特征的参数(TOC、BET比表面积、BJH总孔体积)具有显著的正相关关系。微裂隙与粒间孔隙对页岩中烃类的运移最有利。     

黔北镇远牛蹄塘组黑色页岩沉积环境与有机质富集关系

通过矿物组分、主量元素、微量元素、碳氧同位素等特征,分析了黔北地区镇远县ZX井牛蹄塘组黑色页岩的岩相类型和不同岩相页岩的沉积环境及其与有机质富集间的关系。结果表明,牛蹄塘组下段以硅质页岩为主,TOC含量4.96%～10.10%;上段以富泥硅质页岩为主,TOC含量1.43%～9.04%。下段硅质页岩沉积于水流停滞的深水陆棚环境,沉积古水体为贫氧的还原状态;上段富泥硅质页岩沉积时期,仍为贫氧的还原环境,但水体滞留程度、还原性较下段硅质页岩沉积期弱。贫氧的还原环境是影响牛蹄塘组黑色页岩有机质富集的主要因素,热液作用和陆源碎屑对牛蹄塘组黑色页岩有机质富集的影响较小。     

Organic matter maturity and oil/gas prospects in Middle-Upper Proterozoic and Lower Paleozoic carbonate rocks in northern China

Middle-Upper Proterozoic and Lower Paleozoic carbonate formations in northern China are well developed with an accumulative thickness of 6000–1400 m. Both seepages and oils have been found in the outcrops and drilling wells. The maturity of organic matter in these carbonate formations in obviously lower than that in southern China, as viewed from reflectance (R°), H/C (atomic ratio), the amount and distribution of hydrocarbons,T _max°C and so on.T _max°C may be used as a principal index for determining the maturity of organic matter in carbonate rock-covered areas. According to the results of themeasurement ofT _max°C andR° for natural samples and simulating experiments on bitumens from carbonate rocks, the limitation values for oil and gas have been estimated at 455°C (R°=1.35) and 476°C(R°=2.25), respectively. On this basis, the map of organic matter maturity for the Middle-Upper Proterozoic, Ordovician, Cambrian and Carboniferous of northern China has been compiled. It has been proposed that prospects of both oil and gas are expected, with oil and condensate dominant in the Ordovician, and condensate and dry gas in the Middle-Upper Proterozoic. The Cambrian is intermediate between them.     

Geochemistry of organic matter and elements of black shale during weathering in Northern Guizhou,Southwestern China: Their mobilization and inter-connection

Different from previous studies on effect of weathering upon geochemical variation along a single weathered profile, this paper provides a new methodology validated by comparing a weathered outcrop samples and their stratigraphic counterpart un-weathered core samples in a nearby shallow borehole. This outcrop and borehole penetrated the Ordovician-Silurian Wufeng–Longmaxi shales, located in the same anticline structure in the northern part of Guizhou Province, Southern China. The mineral composition, major, trace and rare earth elements (REEs) composition and Rock-Eval parameters of outcrop and core samples were analyzed and compared. Organic matter (OM) was observed in the microscope and extracted for elements analysis. The results show that short-term weathering still has significant influence on OM, mineral and elemental composition of black shales. The elements composition shows the outcrop profile was moderately weathered. The REEs compositions do not alter much during weathering process and the REEs composition and their relative ratios still are valid for rock origin determination. The OM, mainly composed by graptolite and bitumen, even entering the highly-over thermal maturity, is still sensitive to the weathering with a systematic loss 30–50% of TOC along the outcrop profile, which suggests that the OM consumption is predominantly controlled by weathering duration and the distance from the weathering surface. In turn, OM has significant influence on the trace elements transportation behavior during weathering. Some trace elements associated with the OM such as V, Cr, Th, U, Ni and Co, change significantly in their absolute concentration during weathering, but their relative ratios do not necessarily change too much and might be still reliable proxies for paleo-environmental determination. The mobility of shale minerals during weathering is in the following order: plagioclase?>?potassium feldspar and dolomite >pyrite and OM. Short-term weathering can also result in considerable transportation of elements and significant variation of minerals content in black shale, which may pose potentially high environmental and engineering risk in the regions rich in black shale.     

三江盆地下白垩统穆棱组页岩气成藏地质条件研究

采用有机地球化学分析测试、X衍射荧光分析、高压压汞、扫描电镜、低温氮气吸附等方法,对三江盆地下白垩统穆棱组暗色泥页岩页岩气成藏地质条件开展系统研究,研究结果表明穆棱组暗色泥页岩分布面积较广泛、累积厚度大、TOC含量中等,有机质主要处于成熟-过熟阶段,以Ⅱ2型干酪根为主,说明有机质已进入大量产气阶段;泥页岩中石英、长石及碳酸盐等脆性矿物含量较高;存在一定量的中孔、大孔和微裂缝,为低孔隙度、低渗透率的孔隙结构类型。据现有钻探资料,充分显示了下白垩穆棱组统暗色泥页岩较好的含气性,与美国主要页岩油气产区和中国发现的陆相页岩气层段相对比,三江盆地穆棱组各项参数达标,具有较好的页岩气勘探潜力。     

贵州下石炭统旧司组页岩气地质特征及有利区优选

贵州下石炭统旧司组作为页岩气新区新层系勘探重点,近年来虽开展了大量的页岩气地质调查工作,但勘探效果甚微。本文在大量露头、钻井和测试分析资料的基础上,对其页岩空间展布特征、地球化学特征、页岩气储集特征和含气性特征进行详细分析,发现旧司组主要沉积于台盆和泻湖环境,黔西南地区干酪根类型主要为Ⅱ1和Ⅱ2型,在黔南地区主要为Ⅰ型,TOC主要分布于1%～2%。Ro值主要分布于1%～2.5%,区内热液矿物或温泉的影响不具区域性。页岩中石英含量多＞40%。旧司组下段页岩孔隙以宏孔为主,上段页岩孔隙呈中、宏孔并存。孔隙度主要分布2.0%～10.0%,储集性能中等。黔南地区目标层含气性良好,以吸附气为主。黔西南地区目标层以游离气为主,其含气性受断裂和目标层所处应力状态控制。在此分析基础上,结合勘探实践经验,采用综合信息叠合法初步优选出：望谟-紫云-罗甸、罗甸-克度和蟠龙-勺米3个有利勘探区,有利区面积约为1 448 km²。