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.     

Multivariate analysis of ATR-FTIR spectra for assessment of oil shale organic geochemical properties

In this study, attenuated total reflectance (ATR) Fourier transform infrared spectroscopy (FTIR) was coupled with partial least squares regression (PLSR) analysis to relate spectral data to parameters from total organic carbon (TOC) analysis and programmed pyrolysis to assess the feasibility of developing predictive models to estimate important organic geochemical parameters. The advantage of ATR-FTIR over traditional analytical methods is that source rocks can be analyzed in the laboratory or field in seconds, facilitating more rapid and thorough screening than would be possible using other tools. ATR-FTIR spectra, TOC concentrations and Rock–Eval parameters were measured for a set of oil shales from deposits around the world and several pyrolyzed oil shale samples. PLSR models were developed to predict the measured geochemical parameters from infrared spectra. Application of the resulting models to a set of test spectra excluded from the training set generated accurate predictions of TOC and most Rock–Eval parameters. The critical region of the infrared spectrum for assessing S1, S2, Hydrogen Index and TOC consisted of aliphatic organic moieties (2800–3000 cm⁻¹) and the models generated a better correlation with measured values of TOC and S2 than did integrated aliphatic peak areas. The results suggest that combining ATR-FTIR with PLSR is a reliable approach for estimating useful geochemical parameters of oil shales that is faster and requires less sample preparation than current screening methods.     

鄂尔多斯盆地海陆过渡相富有机质泥页岩特征及页岩气意义

以鄂尔多斯盆地石炭系-二叠系海陆过渡相富有机质泥页岩为研究对象,通过岩石热解分析、岩石抽提和族组分分析、有机元素分析以及煤岩光学分析等方法,对泥页岩中有机质丰度、类型、热成熟度、生烃潜力等地球化学特征参数进行测试;利用扫描电镜、X射线衍射、物性测试等手段,对泥页岩中矿物组成、孔渗特征等储层评价参数进行分析。研究结果表明：鄂尔多斯盆地海陆过渡相地层中泥页岩分布广泛,埋藏偏深,单层厚度较薄,但累计厚度大;泥页岩中有机碳(TOC)含量平均为2.5%,丰度较大;有机质母质中干酪根类型主要为Ⅲ型;镜质体反射率(Ro)平均为1.2%,热演化程度达到中高成熟阶段;具有较大的生烃潜力(S1+S2);同时,石英、长石等脆性矿物含量较高;发育多种孔、缝类型;保存条件良好,为页岩气提供有利的成藏环境。     

贵州织金下寒武统黑色页岩矿物岩石成分及资源利用特征

通过野外采样、化学分析、电子探针(EPMA)和X射线衍射(XRD)分析等手段,研究了贵州织金地区黑色页岩矿物成分、化学组分、微量元素、稀土元素特征。研究区矿样化学成分以SiO_2和Al_2O_3为主,且具有高K低Na的特征。电子探针和X射线衍射分析表明,研究区黑色页岩主要矿物组成有石英、粘土矿物、白云石及黄铁矿等。织金黑色页岩中Pb、Ni、U、V、Cr等金属元素存在不同程度的富集,稀土元素总量为153.2×10~(-6)~224.89×10~(-6),属轻稀土元素富集型。同时从多金属层、页岩气、页岩提钾及近底部含磷铀矿资源等方面讨论了织金黑色页岩资源化利用。织金黑色页岩多金属层含有Mo、V、Ni、Ag及U等多金属元素,具综合利用价值;其中有机碳含量达到页岩气开发大于2%的条件,可进一步开展研究;页岩中伊利石含量较多,可提取黑色页岩中的钾制备含钾复合肥;黑色页岩底部与磷矿层接触带产出磷铀矿,主要为胶状磷铀矿,接触带可作为铀矿找矿的标志层。     

临兴地区海陆过渡相页岩及页岩气地球化学特征

为揭示鄂尔多斯盆地东缘上古生界海陆过渡相页岩及页岩气地球化学特征,选取临兴地区页岩样,开展薄片鉴定、全岩和黏土含量、扫描电镜、有机碳、岩石热解、干酪根显微组分和干酪根碳同位素测试,分析页岩解吸气的气体组分和碳同位素组成。结果表明:临兴地区过渡相页岩矿物组分主要是石英和黏土矿物,含少量方解石、斜长石、钾长石、白云石和黄铁矿等。受矿物成因、沉积环境等多方面的影响,不同矿物组分与有机质赋存方式各异。石英与有机质存在2种赋存方式,黏土矿物存在3种赋存方式,黄铁矿存在4种赋存方式。有机质类型为Ⅱ₂–Ⅲ型,有机碳含量平均值大于2.0%,干酪根碳同位素介于–24.5‰~–23.2‰。镜质体反射率介于0.92%~1.30%,t_max值介于427~494℃,有机质热演化达到成熟阶段。页岩气中烃类气以甲烷为主,含有少量乙烷、丙烷,总体属于干气。甲烷碳同位素均值为–40.0‰,介于海相页岩气和陆相页岩气甲烷碳同位素之间;乙烷碳同位素值介于–26.8‰~–22.56‰,均大于–29‰,整体呈现出δ13C₁＜δ13C₂＜δ13C₃正碳序列。研究认为,该区页岩具备大量生成页岩气的潜力,页岩气主要来源于上古生界偏腐殖型页岩,属于由干酪根裂解而生成的有机热成因煤成气。      

济阳坳陷古近系沙河街组页岩有机质热演化特征

钻探显示渤海湾盆地济阳坳陷古近系沙河街地层具有良好的页岩油资源潜力,成熟页岩厚度超过1 000 m,其有机质热演化特征备受关注。通过对研究区5口页岩油钻井岩石热解地化参数详细统计和对烃源岩原始有机碳、可转换碳、页岩含油量以及生烃潜力等页岩有机质特征的分析,探讨了页岩镜质体反射率动力学应用范畴。沙河街组（沙三段下亚段和沙四段上亚段）页岩最大热解温度（Tmax）为423～450 ℃,有机质成熟度（Ro）为0.45%～0.94%,平均为0.73%,Ⅱ型烃源岩原始有机碳（TOCo）含量为0.92%～5.67%,平均为4.23%,可转换碳（Cc）比例为51%～63%,平均为59%,页岩含油量(S1)为（10～75）×104 t/km2,平均为39.67×104 t/km2,生烃潜力(S2)为（20～465）×104 t/km2,平均为293×104 t/km2,热解产量指数(PI)为0.03～0.47。综合研究认为,济阳坳陷沙河街组优质烃源岩主要集中在东营凹陷和沾化凹陷,有机质成熟度对页岩油的生成和聚集至关重要,当Ro为0.70%～0.74%时,油气开始大量生成,并且开始排烃。     

鄂尔多斯盆地延长探区陆相页岩气储层特征

结合我国陆相页岩分布特征,以鄂尔多斯盆地延长探区为例,对钻孔岩心样品进行有机地球化学、X射线衍射、孔隙度测定、扫描电镜、气体吸附等多种实验分析,研究陆相页岩气储层特征。结果表明,延长探区延长组陆相页岩厚度较大（平均50 m）,有机质丰度高（平均TOC为4.86%）,有机质类型主要为Ⅱ型,热演化程度处于成熟阶段（R_ran为0.84%~1.10%）;页岩中黏土矿物质量分数高（21.8%~71.5%,平均47.3%）,石英质量分数较低（10.8%~44.9%,平均22.3%）,脆性指数相对较小（27.1%~77.2%,平均49.6%）,表明页岩储层具有脆性和可压裂性;延长组页岩孔隙度主要分布在1%~3%,孔隙类型多样,以粒间孔和粒内孔为主,其次是晶间孔、微裂缝、溶蚀孔和有机质孔,为页岩气赋存提供了储集空间;延长组页岩总含气量为1.60~6.67 m3/t,显示出较好的含气性。      

荆门探区五峰组–龙马溪组页岩储层特征及甜点层段评价

为进一步明确荆门探区五峰组—龙马溪组页岩气资源潜力,优选甜点层段,以X井五峰组–龙马溪组一段页岩为主要研究对象,利用干酪根薄片、X衍射、核磁共振、微纳米CT扫描及地化分析等多种测试手段,结合测井解释成果,从岩石学、有机地球化学、矿物组成、孔隙类型及结构、物性及含气性等方面,系统评价五峰组—龙一段各小层储层特征,以优选甜点层段。结果表明:五峰组—龙一段以硅质页岩为主,主要形成于深水陆棚相还原环境,优质页岩段页岩气品质较高,有机地化特征优越;多手段测试孔隙率与渗透率均具有正相关特征,饱和水页岩核磁共振T2谱可分为2类5型,不同类型T2谱所反映的页岩孔径分布特征具有差异性,孤立孔主要存在于小于2 nm的微孔中,占比非常小;基于储层特征评价,优选出龙一$_1^1$—龙一$_1^2$小层为一类储层,五峰组上段和龙一$_1^3$小层为二类储层,龙一$_1^4$小层为三类储层,富碳高硅页岩段的五峰组上段—龙一$_1^3$小层(厚度约17.7 m)为页岩气甜点层段,研究成果可为荆门探区页岩气勘探开发确定水平井的靶体层段提供参考依据。      

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。     

Geochemical and petrographic characterization of organic matter in the Upper Jurassic Madbi shale succession (Masila Basin,Yemen): Origin,type and preservation

The Upper Jurassic Madbi Formation, located in the Masila Basin, eastern Yemen, represents the major source rock in this basin. Organic rich shales from two oilfields (Kharir and Wadi Taribah) were analysed to evaluate the type and origin of the organic matter and to determine the factors controlling its deposition. This study is based on geochemical analyses of whole rock (total organic carbon content, Rock-Eval pyrolysis and carbon isotope data) and petrographic analyses on organic matter (kerogen maceral composition and palynofacies) by optical and scanning electron microscopy. Organic petrographic composition of kerogen shows that the Madbi shale is characterized by high amounts of organic matter, consisting predominantly of yellow fluorescing amorphous organic matter and alginite of marine origin. Terrigenous organic materials such as vitrinite, spores and pollen are present in low quantities. The predominance of marine plankton, as indicated by visual kerogen analysis, is consistent with reported carbon isotopic values. It appears that the high amounts of organic matter in the Madbi shale succession might be mainly due to good preservation under suboxic–anoxic conditions. Consequently the Madbi shales possess very good petroleum generative potential, owing to high content of hydrogen rich Type II and I oil prone kerogen.     

Effect of a dolerite intrusion on triterpane stereochemistry and kerogen in Rundle oil shale,Australia

Stereochemical changes of triterpanes present in extracts from an immature oil shale sequence intruded by a 3-m dolerite sill have been studied by gas chromatography-mass spectrometry (GC-MS). The steric configuration of the hopanes was observed to change from one dominated by the thermally less stable 17β(H), 21β(H) configuration at some distance from the intrusion, to one dominated by the thermally more stable 17α(H), 21β(H) and 17β(H), 21α(H) configurating in the immediate vicinity of the intrusion. In addition, severe alteration of the kerogen appeared to have taken place as a result of the contact metamorphism, and high concentrations of extractable organic matter were observed below the intrusion. Characterization of the kerogens by Curie-point pyrolysis has enabled the effects of the intrusion on the shales to be monitored.     

The kerogen type, depositional environment and maturity, of the Irati Shale, Upper Permian of Paraná Basin, Southern Brazil

Two samples from the upper and lower horizons of the Irati oil shale of the Paraná Basin, Brazil were sampled in a single borehole, and analysed using organic petrography and geochemistry. The results are interpreted in terms of the kerogen type, maturity and depositional environment of the two horizons.Organic petrography shows the oil-shales to be composed of a mineral groundmass, mainly clay minerals, carbonate and pyrite, associated, and sometimes impregnated, with fluorescing organic material and disseminated phytoclasts. Humic material is fairly rare and mostly present as very small particles. The liptinitic particles are mostly alginite (A and B), sporinite and more rarely resinite. Reflectance measurements (upper seam = 0.34% R₀; lower seam = 0.40% R₀) indicate an equivalent rank of lignite/sub-bituminous coal (ASTM), i.e. immature with respect to oil and gas generation. Different organic geochemical methods (Rock-Eval pyrolysis, solvent extraction, GC and GC-MS) demonstrate both samples to be immature, rich oil-shales (100–114 kg/ton) containing Type I kerogen, of a dominantly bacterially-degraded algal origin deposited in a lacustrine environment. The presence of Botryococcus suggests deposition under fresh/brackish water conditions.A tentative interpretation of the extract and vitrinite reflectance data suggests a maximum paleo-burial of between 1.3 and 2.8 km for the analysed section of the Irati Formation.     

柴北缘团鱼山地区中侏罗统石门沟组油页岩有机地球化学特征及古湖泊条件

根据Leco（莱科）、岩石热解、GC（气相色谱）和GC-MS（气相色谱/质谱）等分析,开展了柴达木盆地北缘团鱼山地区中侏罗统石门沟组油页岩有机地球化学特征研究,探讨了油页岩的生烃潜力、有机母质来源、沉积环境及成矿差异。结果表明：石门沟组页岩段共发育3层油页岩（自下而上分别为油1、油2和油3）,油页岩w（TOC）较高,平均值为8.16%,有机质类型为Ⅰ型和Ⅱ₁型,整体生烃潜力较好,且油1、油2的生烃潜力高于油3;样品中检测出丰富的正构烷烃、类异戊二烯烷烃、甾类化合物、萜类化合物和芳香烃化合物,其中,正构烷烃呈单峰式分布,主峰碳数为nC₂₃或nC₂₇,Pr/Ph值为0.20~1.08,油1、油2的C₂₇/C₂₉值、芳基类异戊二烯烃、藿烷和藿烯质量分数明显比油3高,揭示油1、油2形成于强还原条件,有机母质来源以低等水生生物为主,油3形成于弱还原-还原条件,有机母质来源具有陆源高等植物与低等水生生物双重生源特征。结合油页岩特征的差异及古湖泊条件,说明较深的湖水并不是形成优质油页岩的必要条件,藻类、细菌等提供优质有机质的生物输入以及底层水的强还原条件更有利于优质油页岩的形成。     

黔北地区牛蹄塘组页岩气成藏条件及有利区评价

为评估黔北地区下寒武统牛蹄塘组页岩气资源潜力,根据井下岩心和露头岩样的地球化学实验分析结果,对黔北地区牛蹄塘组页岩气成藏条件进行了研究,并评价了该区页岩气成藏的有利区。研究表明:黔北地区牛蹄塘组页岩主要形成于深水陆棚相沉积,页岩埋深适中(<3 000 m),富有机质页岩厚度较大(30~110 m),有机碳含量高(平均TOC>3.0%),有机质类型主要为Ⅰ型,热演化程度高(R_o>2.0%,为过成熟),页岩储层物性为低孔渗,发育大量的微米-纳米级孔裂隙,富含石英等脆性矿物(平均含量>40%),页岩含气量较高(平均1.5 m3/t),具备良好的页岩气成藏条件。在上述基础上,提出东南部的石阡-余庆-施秉一带为黔北地区牛蹄塘组页岩气成藏有利区。      

淮南煤田山西组泥页岩微量元素地球化学特征及其意义

泥页岩中微量元素特征对反演泥页岩形成时的沉积和古地理气候条件具有重要意义。采集淮南煤田山西组泥页岩样品,利用ICP-MS对泥页岩中微量元素进行了测试分析,探讨了研究区山西组泥页岩中微量元素的地球化学特征及其意义。结果表明,B、Cr、U、Ga、Li、Sn、Pb、Mo、Th、W等元素富集,Cd、Co、Cu、Ti、Zn、Sc、Ba、Mn、Ni、Sr等元素亏损;揭示淮南煤田山西组形成于温暖湿润和半咸水-高咸水的沉积环境中,沉积体系为开放型,体系内为弱氧化-还原环境,其中以弱还原-还原环境为主,且表现出从早期弱氧化到中后期的还原环境的演化特征;依据U/Th、Ni/Co、Sr/Cu、B/Ga、Sr/Ba、TOC等地球化学参数结果推测,盐度和氧化还原条件受到多种因素的影响,有机质的原始堆积量是影响山西组泥页岩中有机质含量的主要因素,而盐度和氧化还原条件影响有机质中各显微组分含量。研究区温暖湿润的气候和较为还原的环境为有机质的堆积和保存提供了有利条件,为页岩气的成藏提供了物质基础。      

Organic geochemical evaluation of Cretaceous shale samples from the Orange Basin,South Africa

Organic geochemical evaluation of thirty-two Aptian to Campanian shale samples from seven wells drilled on the shelf of the Orange Basin (southwestern Atlantic margin) was carried out in order to determine their origin, depositional environment, thermal maturity and hydrocarbon potential. The shale samples, selected to represent highstand, lowstand and transgressive systems tracts, were analysed by Rock–Eval pyrolysis for total organic C characteristics and by gas chromatography (GC) and gas chromatography–mass spectrometry (GC–MS) for n-alkanes, aliphatic isoprenoid hydrocarbons and biomarkers (steranes, hopanes and tricylic terpanes). For most of the shale samples Rock–Eval data, hydrogen (HI) and oxygen index (OI) point to mainly Type III terrigenous organic matter. Only a few samples of Turonian age reveal a higher proportion of marine organic matter being classified as Type II/III or Type II. Biomarker parameters suggest that the samples are deposited under suboxic to oxic environmental conditions. Rock–Eval data and biomarker maturity parameters assign for most of the samples a maturity level at the beginning of the oil window with some more mature samples of Aptian, Albian and Cenomanian age. The hydrocarbon generation potential is low for most of the shelf shales as indicated by the S2/S3 ratio and HI values. Exceptions are some samples of Turonian and Aptian age.     

北部湾盆地流二段油页岩地球化学特征及成因

北部湾盆地涠西南凹陷和乌石凹陷流二段普遍发育油页岩。有机地球化学分析表明,北部湾盆地流二段油页岩具有高的有机质丰度,油页岩的有机碳含量下限为3%,含油率介于3.5%~10%,达到中等和优质油页岩矿品级,同时属于优质烃源岩。全岩有机显微组分、干酪根镜检和热解等分析表明,北部湾盆地流二段油页岩藻类含量丰富,藻类是有机质的主要来源,有机质类型主要为腐殖—腐泥型,部分为腐泥型,以湖相腐殖—腐泥型油页岩为主,部分为湖相腐泥型油页岩。流二段油页岩中镍和钼等微量元素含量普遍较高,镍和钼的含量与有机碳含量之间存在很好的正相关关系,说明流二段油页岩形成时期北部湾盆地具有富营养湖泊特征。北部湾盆地流二段油页岩中还原硫含量高,普遍大于1%,流二段油页岩形成于还原的沉积环境,具有很好的有机质保存条件。高有机质生产力及湖侵体系域顶部和高位体系域底部的中深湖还原环境共同控制了北部湾盆地流二段油页岩的发育。     

Characterization of Bulgarian oil shale kerogen revealed by oxidative degradation

A 13-step alkaline permanganate degradation of Bulgarian oil shale kerogen concentrate at ambient temperature was carried out. A high yield of oxidation products (90.1%) and a low yield of gaseous products (2.79%) were obtained. IR and ¹H NMR spectroscopic studies have shown that two significantly different types of high molecular products are present in kerogen. Further oxidation of these structures leads to the formation of low molecular aliphatic and aromatic acids, proven by gas chromotography (GC) and gas chromatography-mass spectrometry (GC-MS). The data obtained at these mild conditions allow us to acquire detailed information about the aromatic structures and polymethylene chain lengths in kerogen.The 5-step oxidation of the kerogen at 90 °C provides information about stable aromatic structures. Soluble and insoluble polyfunctional acids in acid medium have close molecular masses and spectral characteristics. The amount of benzene and naphthalene carboxylic acids is 11.3% of the organic matter of the oil shale.     

准噶尔盆地吉木萨尔地区二叠系芦草沟组油页岩地球化学特征与成矿条件

【研究目的】本文旨在通过对比准噶尔盆地吉木萨尔地区二叠系芦草沟组高品位和低品位油页岩的品质和成因差异,揭示高品位油页岩的特殊成矿条件。【研究方法】对吉木萨尔地区两个剖面采集的露头样品,进行TOC、热解、含油率、微量、稀土元素测试,从而开展高品位和低品位油页岩有机地球化学特征,微量稀土元素特征及成矿条件差异分析。【研究结果】研究区高品位油页岩有机质类型为I型;低品位油页岩有机质类型为I-II1型。高品位和低品位油页岩中B、Ba、Cr、Nb、Sr、V、Zr等微量元素含量差异明显,高品位油页岩中各稀土元素平均含量和各样品稀土元素分布区间都小于低品位油页岩,且外源元素富集程度也相对更低,显示了更少的陆源碎屑输入。微量元素比值显示,研究区油页岩形成于温暖湿润气候,淡水—半咸水,还原环境。高品位油页岩与低品位油页岩相比,形成时水体盐度值更大,有机质生产力更高。【结论】温暖湿润气候背景下,相对较少的陆源碎屑供给,减少了对有机质的稀释和氧化破坏,同时较高的水体盐度值更利于水体分层,从而形成一个长时间的还原环境,再加上更高的有机质生产力,从而形成了高品位油页岩。     

A comparison of organosulphur compounds produced by pyrolysis of asphaltenes and those present in related crude oils and tar sands

Asphaltenes and NSO fractions from a variety of oils and tar sands have been characterized by pyrolysis-gas chromatography (Py---GC) using both flame ionization and flame photometric detectors. Organosulphur compounds were not always produced by pyrolysis of the asphaltenes isolated from the biodegraded tar sand extracts although pyrolysis of the NSO fractions produced a series of thiophenes from all of the samples examined. These observations suggest that under certain conditions, asphaltene fractions may be affected by biodegradation, leading to preferential removal of the sulphur containing compounds. In addition, it was observed that Py---GC of asphaltenes permitted oils to be differentiated on the basis of their source rock lithology. Oils derived from carbonate source rocks produced thiophene/benzothiopene ratios <1 whilst the same ratio was >1 for oils derived from shales. Thiophene/dibenzothiophene ratios could be used in a similar manner.