河北省下花园地区下马岭组碳酸盐生油岩热模拟实验

对下马岭组灰岩进行了热模拟实验,对碳酸盐岩腐泥型有机质的热演化规律进行了研究,划分了其演化阶段,给出了成熟度指标和各阶段油气产率.研究表明,矿物对有机质热演化的影响,在成熟阶段主要表现为催化作用;在高过成熟阶段则主要表现为对干酪根裂解、脱氧和缩合有阻碍作用.沥青“C”的某些成熟度指标可较好地反映有机质成熟度;在缺乏镜质体时焦沥青反射率可作为有效的成熟度指标.此外还对比了岩样和干酪根的模拟结果,以及沥青“A”和“C”的差异.     

页岩有机质热演化生烃成孔及其甲烷吸附机理研究进展

对生物体形成干酪根过程、页岩干酪根生成油气机理、页岩有机质孔隙演化特征、有机质孔隙内气水分布特征进行了综述和评论.认为生物化学生气阶段通过细菌作用、缩聚作用形成干酪根,因干酪根脂族C-H键释放而形成脂族分子间孔;热催化生油气阶段通过热解聚作用形成沥青质、液态烃及剩余干酪根,此阶段沥青大量裂解为液态烃而形成边缘油孔(液化孔);热裂解生凝析气阶段,液态烃裂解为湿气,有机质孔隙以边缘(或内部)气孔为主;深部高温生气阶段转化为干气,此过程干酪根芳族C-H键释放,有机质孔隙以芳族分子间孔、气孔为主.同时,页岩干酪根热演化各阶段有机质孔隙内均有水的参与,表现出固-液界面作用.此工作以期为我国页岩气进一步勘探开发提供理论依据,也对页岩气产气规律的认识具有指导意义.     

东濮凹陷北部地区古近系油型气成因类型及分布特征

以热压模拟实验模拟东濮凹陷干酪根热裂解和原油热裂解过程,分析干酪根热裂解气和原油裂解气组分特征的差异,以此建立干酪根热裂解成因气和原油裂解成因气的判识方法;结合东濮凹陷北部地区天然气碳同位素及天然气组分数据,对研究区油型气进行划分,进而探讨干酪根热裂解气与原油裂解气的分布特征。结果表明,研究区古近系油型气分为干酪根热裂解气与原油裂解气,干酪根热裂解气具有相对较高的C1/C2值和较低的C2/C3值特征,而原油裂解气则与之相反。干酪根热裂解气和原油裂解气的分布存在明显差异:前者分布范围更广,后者更近于洼陷中心分布,两者分布的差异性与其生成及成藏条件差异有关。根据干酪根热裂解气与原油裂解气分布特点,推测在邻近洼陷中心区具有良好的干酪根裂解成气及原油裂解成气的条件和油型气勘探前景。     

鄂尔多斯盆地宜川地区上古生界烃源岩评价

依据氢指数（HI）、降解率（PC/TOC）等两个方面的地球化学指标,按照煤系地层烃源岩有机质类型划分标准,对研究区的山西-太原组烃源层的有机质类型作剖析,进行上古生界烃源岩系统评价。研究认为,本溪组烃源岩主要是泥岩,有机质丰度平均2.51%,泥岩干酪根母质类型主体属腐殖型干酪根,即Ⅲ型干酪根;太原组暗色泥岩有机质丰度平均2.26%,煤层比较发育,有机质丰度平均81.66%;山西组的泥岩比较发育,泥岩有机质丰度平均2.26%,煤层有机质丰度平均72.66%。本区上古生界干酪根显微组分都以镜质组为主,显示干酪根母质为腐殖型,即Ⅲ型干酪根,热成熟度演化较高,Ro都大于2.5%,Tmax为490℃以上,表明泥岩已达到过成熟阶段,本区暗色泥岩及煤层属中等—好气源岩,此次烃源岩的认识对该区下一步的勘探提供重要的依据。     

用红外光谱表征干酪根和煤的芳碳量

干酪根和煤红外光谱中的芳碳含量常以1600cm~(-1)频带来表征.但该频带的强度受芳碳骨架化学环境和结构的强烈影响.用苯并菲、茬、二羟基蓁、二苯酮和联苄等6种模型化合物进行红外光谱分析发现,1600 cm~(-1)频带因芳环稠化而迅速减弱,因邻接含氧基团而显著增强.对不同类型干酪根的热模拟系列产物进行了红外光谱和固体~(13)C核磁共振波谱的综合研究.结果表明,1600 cm~(-1)的摩尔吸光系数ε_1600有随演化加深而下降的趋势,尤以煤系干酪根为甚,与模型化合物的结果相符.因此,吸收系数K_1600可用以区分干酪根的类型,但不宜用作其成熟度的参数.     

页岩纳米级孔隙结构特征及热成熟演化

以中、上扬子地区下古生界海相和中生界陆相页岩为研究对象,运用氩离子抛光-场发射扫描电子显微镜技术和氮气吸附实验测试技术对页岩储层的纳米级孔隙发育特征及热成熟演化进行探讨。结果表明:页岩主要发育了有机质孔、粒间孔、粒内孔和微裂缝等4种孔隙类型;TOC和Ro是控制页岩纳米级孔隙发育的主要因素;对于高演化页岩,不同干酪根类型的有机质孔隙发育程度的大小次序为Ⅰ型Ⅱ型Ⅲ型;石英和黏土矿物通过控制TOC的变化对纳米级孔隙发育和分布产生间接影响;页岩热成熟度演化影响页岩孔径分布和微孔、中孔和大孔相对含量的变化,在高—过成熟阶段,与有机质有关的微孔、中孔呈不断增加的趋势,在极高成熟度阶段,页岩大孔转变为中孔和微孔,有机质孔隙变小,纳米级孔隙体积呈现出先增加后减小的趋势;页岩中干酪根、可溶沥青热裂解生气作用和甲烷化作用可能是页岩有机质纳米级孔隙形成的主要原因。     

扬子地块西北缘、西南缘卡林型金矿的干酪根与金矿化关系

根据干酪根的元素组成及其他的矿床地质，地球化学特征确定，扬了地块西北缘，西南缘的卡林型金矿床的干酪根属腐泥干酪根，干酪根的元素组成和成熟度是判别大型卡型金矿床和小型卡林型金矿床或矿点的重要标志，大型卡型金矿床的干酪根，碳的平均含量为４２．５５％。氢的平均含量为１．６９％，氧的平均含量为５．０３％，小型卡林型矿床或矿点的干酪根，碳的平均含量为７７．２３％，氢的平均含量为１．２２％，氧的平均含量为４．     

评价干酪根生油气量的一种新方法

用压力差示扫描量热仪(PDSC)研究了我国茂名、抚顺、黄县油页岩干酪根(Ⅰ,Ⅱ型)及黄县褐煤(Ⅲ型)在热降解时的化学结构变化。试验中发现,在氧气压力为1.5MPa时,各种干酪根的PDSC图谱都出现两个放热峰。由放热峰的积分面积可计算出各干酪根的表观芳碳率。由此提出了计算干酪根生油、气量的新方法,可根据干酪根在热降解时的“残留脂碳率”与“干酪根质量系数”的演化图计算出生油岩的生油量和生气量,也可以根据干酪根热降解时的脂构碳、芳构碳的分布计算干酪根生油、气量的简化模式,由脂构碳的热解动力学参数计算出生油岩的油气生成量。     

辽河滩海烃源岩地球化学特征分析

通过评价滩海地区烃源岩的有机质丰度,用干酪根镜下显微组分鉴定．干酪根元素,干酪根碳同位素,生物标志化合物等几种方法确定烃源岩的有机质类型以及有机质成熟度的分析,得出结论滩海地区主力烃源岩为沙河街级三段,其次为沙河街组一二段,潍海西部凹陷和东部凹陷生油门限存在差异,滩海西部凹陷生油门限为2800m左右,滩海东部凹陷为2850m左右。     

长岭断陷南部地区断陷层油气成藏机制及勘探潜力

利用天然气组成、轻烃指纹、碳同位素和生物标志化合物以及储层流体包裹体等地球化学特征,结合地质条件以及生烃史-热史模拟研究长岭断陷南部的龙凤山地区油气成因及成藏过程,揭示其油气成藏机制。结果表明:龙凤山地区断陷层天然气属于腐殖型和腐泥型的混合气,且为裂解气和干酪根热降解气组成的混合气,油气源主要为本地的沙河子组烃源岩,原油成熟度低于天然气,为同一油源不同热演化阶段的产物,属于次生凝析气藏,成藏表现为"近源多向供烃,复合输导,早期干酪根热降解成气与晚期原油裂解成气"的多期成藏模式;长岭南部地区发育优质烃源岩、营城组末期形成的反转构造提供了圈闭条件,具备较好油气输导条件、存在多期油气充注,油气勘探潜力大。     

Origin of immature sulfur-rich oil in Jianghan oil field

Chemical structure of immature sulfur-rich kerogen and composition of immature sulfur-rich crude oil in Jianghun oil field have been studied. In molecular level, crude oil differs from thermolysed and chemolysed products of kerogen but does resemble the bitumen in immature sulfur-rich source rock. Therefore, immature sulfur-rich oil may be derived from the expelling of bitumen rather than from thermal cracking of kerogen.     

Simulation experiments for evolution of fatty acids in immature source rocks

The anhydrous, hydrous and bitumen-extrac- ted simulations were carried out for the immature source rocks from the Liaohe sag. It has been shown from the result that with increasing temperature in simulation experiments, the fatty acids content decreased at first and then increased. The decrease of fatty acids in immature rocks is presumably related to alkanes generation in immature oils, whilst the increase may be related to the fact that some additional fatty acids are generated from kerogen and the tightly bound fatty acids in kerogen are released as bound fatty acids in kerogen and unbound fatty acids in bitumen. The fact that the bitumen generated from kerogen contains fatty acids has demonstrated that some bound and tightly bound fatty acids in kerogen can be transferred into bitumen. The preferential fatty acids in the immature source rocks are found to be mono-carboxylic acids with longer chains, whilst krogen contains relatively more di-carboxylic acids. It has been found that the fatty acids in immature source rocks can be changed from that with more longer chains to that with more shorter chains when evolution extent has been increased. Based on simulation results and the fact that the majority of fatty acids in immature oils are those with longer chains, it is inferred that the contribution of fatty acids to forming alkanes in immature oils mainly takes place at the evolution stage with R₀ <0.6%. The simulation experiments have also demonstrated that H₂O could promote the generation of fatty acids with more di-carboxylic acids and delay alkanes formation from fatty acids.     

The occurrence of fatty acids in immature source rocks and their distribution characteristics

The fatty acids in extractable bitumen and kerogen of immature source rocks of the Liaohe Basin and Jiyang sag were investigated in this study. The result showed that the bitumen fatty acids were mainly associated with non-hydrocarbon fraction and that the kerogen fatty acids with some tightly bound fatty acids were mainly bounded in a net structure of kerogen by ester bonds. For the investigated source rocks, the fatty acids in bitumen, bound fatty acids and tightly bound acids in kerogen ranged in 0.01%—0.073.9%, 0.005%— 0.045 5% and 0.005%— 0.010% respectively. Among the fatty acids analyzed in this study, mono-carboxylic acids, a , w -di-carboxylic acids and hydroxy acids accounted for 70%—100%, 0%—30% and <10% respectively. It was also found that the mono-carboxylic acids with longer chains mainly existed in bitumen, and that the a , w -di-carboxylic acids and hydroxy acids mainly existed in kerogen. From above, it was assumed that the mono-car- boxylic acids in bitumen might have played an important role in the hydrocarbon generation from fatty acids in immature source rocks.     

Determining the temperature of petroleum formation from the kinetic properties of petroleum asphaltenes

Knowledge of the timing and location of petroleum formation is important in assessing the extent of available reserves in hydrocarbon-forming basins. This can be predicted from the thermal history of a basin and the kinetic parameters that characterize the thermal breakdown of kerogen in source rocks. At present, the kinetic parameters of kerogen breakdown are experimentally determined using immature rock samples from basin margins, but questions remain about the accuracy of this approach, especially when significant variability is observed within individual source units. Here we show that the kinetics of hydrocarbon generation from petroleum asphaltenes can be used to determine the temperature conditions of the actual source rock at the time of expulsion of the sampled petroleum. This relationship reflects the structural similarity of asphaltenes to the parent kerogen. We expect that our approach may be used as a comparatively simple alternative method for assessing the petroleum generation characteristics of a given basin, which will allow for better estimates of the available oil resources and the risks associated with their exploration.     

Simulation experiment of immature oil genetic mechanism in lake facies of semi-salt water

The Immature calcareous shale in the south slope of Dongying sag, Jiyang depression, plays a significant role in immature oil genesis, and is sampled to make simulation experiment. The geochemical characters of the products of soluble organic matter and kerogen are researched respectively. The yields of the two components and their relations are made out. The contribution ratio between soluble organic matter and kerogen undergoing earty degradation in lake facies of semi-salt water is figured out for the first time, so the research into the genetic mechanism of immature oil is developed.     

绿河油页岩油母电子结构及热稳定性

为充分开发和合理利用油页岩,以绿河油页岩结构模型为基础,采用杂化密度泛函理论（B3LYP）方法,研究了油母的几何结构、键级、键能、前线分子轨道、静电势、核磁等相关性质。结果表明：氧原子部位是该油母结构热裂解和化学反应的主要活性部位,六元环的不规则变形是其开环裂解的主要原因,但饱和烷烃六元环和链状结构的差异对于电子结构没有显著影响。该研究为油页岩炼油技术的改进提供了理论依据。     

The role of sulfur in the pyrolysis of kerogen

Sulfur plays an important role in the generation and evolution of hydrocarbon from organic matter. Here, a pyrolysis experiment in closed system was performed on Maoming oil shales kerogen (Type Ⅰ), Maoming oil shales kerogen added with sulfur ether and Maoming oil shales kerogen added with sulphur. The results suggest that the existence of sulfur can result in: (i) higher yield of hydrocarbons generated from the kerogen; (ii) decrease of the temperature for the maximum generation of heavy hydrocarbons (the C15+ fraction) by 20℃; (iii) decrease of the temperature for the maximum generation of the aromatics fraction by 40℃, and (iv) acceleration of the aromatization process. The pyrolysates from kerogen added with sulfur are similar to the heating products of the sulfur-rich kerogen as reported in the literatures. It seems that the sulfur catalysis is also an important factor that can make the sulfur-rich kerogen generate low-mature oil at the earlier diagenesis stage, except for the weakness of the C-S and S-S bonds.     

盐水介质中煤的早期热解生烃特征和动力学

利用高压釜反应装置，在水介质下对繁峙褐煤进行了低演化阶段的热压模拟实验，考察了碳酸钠盐水介质对热解产物生成过程的影响，探讨了产物的生成特征及动力学。盐水介质的存在，对褐煤热解生烃过程具有一定的催化作用，提高了气态产物和热解沥青的收率，而对热解沥青的进一步热解生油过程几乎没有影响。动力学计算结果表明，在１００℃的地质温度下，碳酸钠介质的存在，可使气态产物和热解沥青的生成速率提高５０％～１００％．碳酸钠碱性水介质的催化作用，可借助于溶剂效应和电子诱导效应理论进行初步的解释。     

塔北轮南地区油气成因与成藏探讨

通过对塔里木轮南地区不同层位、不同部位原油烃类化学组成的剖析 ,认为该区原油至少可分为两种不同的成因类型 ,可能存在多成藏期次 .三叠系、侏罗系原油化学组成与分布均一 ,其与轮南中西部断垒、桑塔木断垒西部奥陶系原油性质极为接近 ,以低分子量正构烷烃占优势 ,重排补身烷与重排甾烷、三环萜烷及Ts不甚发育 ,C2 3 三环萜烷为主峰 ,相对低值C2 7/C2 9甾烷等为特征 (第I类 ) ,奥陶系原油还具有中性氮化合物含量高的特征 ;以两断垒带东部石炭系、奥陶系为代表的原油以高值饱芳比、正构烷烃主峰碳后移、高含量C15 重排倍半萜与重排甾烷、低含量中性氮化合物、C2 0 三环萜烷为主峰、相对高值C2 7/C2 9甾烷、甾烷 /藿烷、Ts/ (Ts+Tm)、三环萜 /五环萜值等为特征 (第Ⅱ类 ) .轮南地区原油类型不同由主系油源不同所致 .烃类与非烃类运移指标反映奥陶系、石炭系原油具有自西而东的运移趋势 ;三叠系原油具有不太明显的由北而南的运移趋势 .烃类指标反映三叠系、侏罗系与同类型奥陶系原油间的运移分馏效应不太明显 ,其可能来自相同的烃源岩但成烃与成藏期不同