海陆过渡相地层有机质纳米孔成因及地质意义——以鄂尔多斯盆地东部山西组为例

海陆过渡相煤系地层已经发现丰富的非常规天然气资源。本文以鄂尔多斯盆地东部山西组煤系地层为例,通过开展微观特征分析及物理模拟实验,查明山西组主要孔隙类型为有机质孔隙、残余原生孔隙、不稳定矿物溶蚀孔、黏土矿物层间孔,认为黏土矿物层间孔和有机质纳米孔隙是页岩储集空间与常规砂岩储层的显著区别;山西组煤系地层广泛发育的有机质纳米孔,经过模拟实验认为形成于早期液态烃裂解气,随着原油沥青化,气泡被固化在沥青条带中形成纳米孔隙;集中发生在晚侏罗世至早白垩世末的异常热事件控制了裂解气生成的强度和范围,在此过程中沥青化产生的有机质纳米孔大幅度提高煤系地层非常规气储集空间和资源丰度。这一认识对于深入了解山西组煤系地层孔隙结构特征及非常规油气地质评价选区具有重要意义。     

页岩能源共生矿产成矿（藏）地质条件研究--以松辽盆地上白垩统青山口组为例

页岩能源矿产已成为国内外研究热点,并掀起一场“页岩革命”,其主要包括油页岩、页岩油、页岩气等非常规页岩能源资源。这套页岩能源矿产与富有机质泥岩密切相关,其在成因上存在一定的联系和共生规律,但成矿（藏）条件又存在明显的不同。松辽盆地上白垩统青山口组发育厚层的暗色泥岩,由于其面积巨大,泥岩中有机质丰度高,埋藏深度差异明显,具备形成页岩能源共生矿产成矿（藏）的地质条件。初步分析认为,松辽盆地青山口组下部暗色泥岩有机质丰度较高,有机质类型主要为I~II₁型,为油页岩成矿,页岩油、页岩气成藏提供足够的有机质来源,其中在松辽盆地东南隆起区,青山口组埋藏较浅（深度＜1 000 m）,有机质热演化程度较低（Ro＜0.7%）,为良好的油页岩成矿场所。埋藏浅的富有机质泥岩可能因微生物活动而形成生物成因页岩气,较弱的成岩压实作用和极为丰富的有机质为页岩气成藏提供足够的空间（孔隙度4%~14%）。从盆地东部的隆起带到中央凹陷区,随着埋深加大（深度＞1 000 m）,热演化程度逐渐增强（Ro:0.7%~1.2%）,基本处于成熟-过熟阶段,有机质大量排烃,为页岩油、页岩气成藏提供足够的来源。异常高压和排烃造孔形成良好的储层,使泥页岩具备页岩油、气成藏的良好条件。因此,松辽盆地可能存在呈环形的页岩能源矿产成矿（藏）规律,其中在东南隆起区和中央凹陷隆起地区为油页岩成矿和生物型页岩气有利成藏带;中央凹陷大部分地区可能为页岩油、热解型页岩气有利成藏带;中央凹陷埋藏最深部位可能发育热裂解型页岩气有利成藏带。     

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。      

High temperature simulation of petroleum formation—IV. Stable carbon isotope studies of gaseous hydrocarbons

Laboratory simulations of petroleum formation were examined by stable carbon isotope studies of five cryogenic distillation fractions of the gases produced by thermal treatment of organic substrates. Simple heat treatment (pyrolysis) of substrates was contrasted with heat treatment in the presence of nickel and vanadium sulfides, ammonia, and water (catalysis). The effect of substrate/catalyst ratio on the isotopic composition of gases was also examined. All reactions were carried out at 440°C, and ambient pressure. Plots of stable carbon isotope ratio versus distillation temperature, for substrates representing marine and terrestrial organic matter, were compared to literature values for natural petroleum accumulations, and to the pyrolysis of Green River oil shale.     

青藏高原北部东昆仑地区三叠系页岩成岩作用及其对储层的影响

青藏高原北部东昆仑地区八宝山盆地作为高原页岩气成藏特征探索的典型区域之一,对影响储层储集性能的关键因素——成岩作用的研究程度很低,不足以更大限度地发挥其勘探价值。基于岩性观察及薄片、铸体薄片、扫描电镜、X-射线衍射等实验分析资料,对该区三叠系页岩成岩作用及对储层的影响开展研究,结果显示,三叠系八宝山组页岩成岩作用共有6类：压实、胶结、黏土矿物转化、交代、溶蚀及有机质热成熟作用。综合有机质成熟度、岩石热解最高峰温、伊蒙混层比中蒙皂石占比、黏土矿物组合、孔隙类型等指标得出：研究区页岩处于中成岩B期-晚成岩阶段。结合各成岩作用对储层孔隙度的影响,研究区压实作用、胶结作用、黏土矿物转化作用易于造成孔隙度的减小,溶蚀作用、有机质热成熟作用易于孔隙度的增大,而交代作用对孔隙影响小。     

海相烃源岩二次生烃潜力定量评价新方法

烃源岩二次生烃的演化过程是残余干酪根热解演化与残留油热裂解转化两个既相互联系又完全不同的物理化学反应过程的叠加。本文利用自制高压釜热压生烃模拟实验装置,采取分阶段连续递进模拟实验方式,以海相烃源岩样品为例分别评价了残余干酪根的生烃潜力与残留可溶有机质转化油气潜力,建立了一套不同起始与终止成熟度海相烃源岩二次生烃潜力的定量评价方法,并首次明确提出了干酪根生油指数KIo、干酪根生气指数KIg、干酪根生烃指数KIh等评价烃源岩生烃潜力的参数,弥补了ROCK EVAL热解评价方法无法分别评价烃源岩在不同生烃演化阶段所生成的“油”或“烃气”潜力的不足。     

松辽盆地北部青一段油页岩地球化学特征及其记录的古湖泊学信息

油页岩地球化学特征及其记录的古湖泊学信息是揭示油页岩成矿富集规律的关键佐证。根据含油率、TOC、岩石热解、元素分析、生物标志化合物检测及有机显微组分分析,精细刻画了松辽盆地北部ZY1井青一段油页岩的地球化学特征,并分析了其记录的古湖泊学信息,探讨了古湖泊对油页岩有机质富集的控制作用。结果表明：青一段发育8层中等偏好品质的油页岩,下部为高品质油页岩富集层段;油页岩的含油率和TOC质量分数相关性极好,处于未熟—低成熟度演化阶段,生烃潜力大;油页岩中含丰富的萜类和甾类化合物,有机质类型主要为Ⅰ型,有机质来源主要为层状藻占优势的湖泊水生生物。地球化学参数指示,青一段下部古湖泊生产力呈现3个低→高的旋回,对应的古湖泊水体盐度呈现为3个半咸水-咸水旋回、古湖泊水体氧化还原性表现为还原-强还原-还原的厌氧环境,其中旋回Ⅱ后期湖泊生产力最高,对应的水体盐度最高、还原性最强。表明湖泊富营养化造成的高湖泊生产力是青一段高品质油页岩有机质富集的物质基础,盐度分层控制下强还原的湖底环境是高品质油页岩有机质富集的良好保存条件。     

海陆相泥页岩气体生成的半封闭模拟实验

明确不同沉积环境下页岩气生成机理的差异性对于页岩气成因机理及页岩气地球化学特征研究具有重要意义.选择低演化阶段的海相（中元古界洪水庄组）和陆相（三叠统延长组长7段）泥页岩进行了半封闭热模拟实验,对其气体产物进行了组分和碳同位素分析.结果表明,洪水庄组页岩产气量要远远低于同温度条件下长7段泥岩的产气量.同时,长7段泥岩气体产物二次裂解程度比较高.洪水庄组页岩有机质母源以生油性为主,长7段泥岩沉积过程受到陆源混入,有机质母源以相对偏生气性为主.热模拟实验条件下黄铁矿转化成磁黄铁矿的过程也可能促进长7段泥岩烃类气的生成.热模拟实验中所用样品的状态,即柱状样或颗粒样,也可能会对气体的裂解行为产生影响.在这种情况下,南方地区页岩气高的甲烷产率以及碳同位素倒转可能与厚层页岩高的油气滞留率有关.      

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。     

油页岩原位开采温度-时间-转化率判识方法及应用

油页岩原位转化开采加热的最终温度、加热时间和最终油气转化率与原位开采的经济成本息息相关。利用Rock-Eval 6型岩石热解分析仪分别获取不同升温速率下的油页岩烃产率-转化率和烃产率-活化能之间的关系,以烃产率为桥梁,建立活化能与转化率的对应关系;在此基础上,依据化学动力学反应原理,将油页岩有机质（干酪根）演化生成油气的过程近似为具一级反应特征的热裂解反应,获取不同转化率条件下温度倒数（1/T）与时间对数（ln t）的关系式,建立油页岩原位转化温度-时间-转化率关系图。以广东茂名盆地油柑窝组油页岩为例,通过上述方法建立了油页岩原位转化开采温度-时间-转化率关系图。由判识关系图可知：加热至350℃开采该区油页岩,转化率达90%需要98 a;加热至200℃开采该区油页岩,在不采取其他措施的情况下即使转化10%也需要147 a。实际情况下,地下油页岩原位受热具有非均质性,加热开采能耗大,通过添加催化剂降低油页岩原位油气转化所需的温度、改善油气产物品质可能是油页岩原位开采技术的一种发展方向。     

Alkene transformations catalysed by mineral matter during oil shale pyrolysis

The effects of mineral matter on the pyrolysis behavior of an Australian aliphatic oil shale (Rundle, aromaticity = 0.21) have been studied. Besides confirming previous reports that mineral matter in highly aliphatic shales reduces the yield of oil from pyrolysis, the results clearly show that some mineral matter components such as montmorillonites and poorly ordered aluminosilicates can reduce the ratio of 1-alkenes to internal alkenes in oils. Isomerization is dependent on the type of aluminium coordination in the mineral matter and the tetrahedral aluminium is most efficient at altering alkene ratios. Although there is no evidence that mineral matter operates through a carbocationic mechanism to reduce the oil yield, the results strongly suggest that such a mechanism operates during alkene isomerization.     

南襄盆地泌阳凹陷陆相页岩油地质特征与评价

南襄盆地泌阳凹陷中部深凹区发育有淡水环境及咸水环境沉积的深湖—半深湖相页岩。该套页岩岩相复杂、类型多、变化快, 可分为泥质粉砂岩、粉砂质页岩、隐晶灰质页岩、重结晶灰质页岩及白云质页岩, 总体富含有机质, 这为陆相页岩油的形成提供了充分的物质基础。研究区页岩具有纵向厚度大、横向分布广、有机质丰度高及类型好、热演化程度适中、脆性矿物含量高及含油气性好等特征, 具备良好的陆相页岩油形成条件。在明确泌阳凹陷具备良好的陆相页岩油形成条件基础上, 进一步开展了陆相页岩油地质评价方法的研究, 提出了一套包含岩石学分析、地质多参数综合评价、有利区带评价等8项关键技术的地质评价方法, 并明确了泌阳凹陷陆相页岩油富集的主控因素及有利目标区, 进而优化部署页岩油水平井, 取得了中国陆相页岩油勘探的重大突破, 展示了中国陆相页岩油良好的勘探开发前景。     

鄂尔多斯盆地南缘铜川地区三叠系延长组长9段浊积岩特征及对有机质富集的影响

通过岩芯观察、岩石薄片粒度分析,在鄂尔多斯盆地南缘铜川地区三叠系延长组9段识别出了浊积岩,并揭示了其垂向上典型鲍马序列组合及沉积特征。同时,对鄂尔多斯盆地延长组长9段的油页岩、富有机质泥岩等样本进行TOC、热解测试,分析了该段浊积岩特征及对有机质富集的特征及影响。结果表明:半深湖--深湖区油页岩、泥岩干酪根类型以Ⅱ1型为主,浊积岩上下层位的泥岩、泥页岩、粉砂质泥岩等干酪根类型主要为Ⅲ型和Ⅱ2型。长9段浊积岩对含油页岩段的有机质富集具有一定影响,浊积岩AB及ABC序列对底部沉积的泥岩、泥页岩有机质含量影响最大,其有机碳含量相对较低;浊积岩DE序列对底部沉积的泥岩、泥页岩有机质含量影响相对较小,有机质含量相对较高。     

Role of minerals in the thermal alteration of organic matter—I: Generation of gases and condensates under dry condition

Pyrolysis experiments were carried out on Monterey formation kerogen and bitumen and Green River formation kerogen (Type II and I, respectively), in the presence and absence of montmorillonite, illite and calcite at 200 and 300°C for 2–2000 hours. The pyrolysis products were identified and quantified and the results of the measurements on the gas and condensate range are reported here.A significant catalytic effect was observed for the pyrolysis of kerogen with montmorillonite, whereas small or no effects were observed with illite and calcite, respectively. Catalytic activity was evident by the production of up to five times higher C₁–C₆ hydrocarbons for kerogen with montmorillonite than for kerogen alone, and by the dominance of branched hydrocarbons in the C₄–C₆ range (up to 90% of the total amount at any single carbon number). This latter effect in the presence of montmorillonite is attributed to cracking via a carbonium-ion [carbocation] intermediate which forms on the acidic sites of the clay. No catalytic effect, however, was observed for generation of methane and C₂ hydrocarbons which form by thermal cracking. The catalysis of montmorillonite was significantly greater during pyrolysis of bitumen than for kerogen, which may point to the importance of the early formed bitumen as an intermediate in the production of low molecular weight hydrocarbons. Catalysis by minerals was also observed for the production of carbon dioxide.These results stress the importance of the mineral matrix in determining the type and amount of gases and condensates forming from the associated organic matter under thermal stress. The literature contains examples of gas distributions in the geologic column which can be accounted for by selective mineral catalysis, mainly during early stages of organic matter maturation.     

Characterization of a Lacustrine Shale Reservoir and the Evolution of its Nanopores: A Case Study of the Upper Cretaceous Qingshankou Formation in the Songliao Basin,Northeastern China

The Songliao Basin is one of the most important petroliferous basins in northern China. With a recent gradual decline in conventional oil production in the basin, the exploration and development of unconventional resources are becoming increasingly urgent. The Qingshankou Formation consists of typical Upper Cretaceous continental strata, and represents a promising and practical replacement resource for shale oil in the Songliao Basin. Previous studies have shown that low-mature to mature Qingshankou shale mainly preserves type Ⅰ and type Ⅱ1 organic matter, with relatively high total organic carbon(TOC) content. It is estimated that there is a great potential to explore for shale oil resources in the Qingshankou Formation in this basin. However, not enough systematic research has been conducted on pore characteristics and their main controlling factors in this lacustrine shale reservoir. In this study, 19 Qingshankou shales from two wells drilled in the study area were tested and analyzed for mineral composition, pore distribution and feature evolution using Xray diffraction(XRD), scanning electron microscopy(SEM), low-pressure nitrogen gas adsorption(N2-GA), and thermal simulation experiments. The XRD results show that clay, quartz, and feldspar are the dominant mineral constituents of Qingshankou shale. The clay minerals are mostly illite/smectite mixed layers with a mean content of 83.5%, followed by illite, chlorite, and kaolinite. There are abundant deposits of clay-rich shale in the Qingshankou Formation in the study area, within which many mineral and organic matter pores were observed using SEM. Mineral pores contribute the most to shale porosity;specifically, clay mineral pores and carbonate pores comprise most of the mineral pores in the shale. Among the three types of organic matter pores, type B is more dominant the other two. Pores with diameters greater than 10 nm supply the main pore volume;most are half-open slits and wedge-shaped pores. The total pore volume had no obvious linear relationship with TOC content, but had some degree of positive correlation with the content of quartz + feldspar and clay minerals respectively. However, it was negatively correlated with carbonate mineral content. The specific surface area of the pores is negatively related to TOC content, average pore diameter, and carbonate mineral content. Moreover, it had a somewhat positive correlation with clay mineral content and no clear linear relationship with the content of quartz + feldspar. With increases in maturity, there was also an increase in the number of carbonate mineral dissolution pores and organic matter pores, average pore diameter, and pore volume, whereas there was a decrease in specific surface area of the pores. Generally, the Qingshankou shale is at a low-mature to mature stage with a TOC content of more than 1.0%, and could be as thick as 250 m in the study area. Pores with diameters of more than 10 nm are well-developed in the shale. This research illustrates that there are favorable conditions for shale oil occurrence and enrichment in the Qingshankou shale in the study area.     

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。     

页岩油化学生热原位转化开采理论与方法

页岩油资源量潜力巨大,作为一种重要的接替能源,寻求页岩油的有效开发与经济利用的途径,对缓解能源供需矛盾具有重大的现实意义。在分析页岩油原位转化/改质各种方法优缺点的基础上,总结了页岩油裂解生烃转化的温度时间条件与结构演化特征,根据物质与能量平衡原理,提出了页岩油化学生热原位转化开采理论与方法,论证了该方法温度水平、热量供给和固相体积变化等技术可行性,提出了关键技术可能突破的工艺路径。得出了如下结论:当前中低成熟度页岩油和油页岩地下原位转化/改质方法主要面临热效率低、污染风险高和储层沉降失稳等瓶颈难题; 提出了页岩油化学生热原位开采理论,采用氧化钙与水反应为有机质原位转化提供热量,通过热量平衡与固相物质平衡分析、高压氧化钙水解试验,证明了该理论方法的技术可行性和经济性; 建立了页岩油化学生热原位转化开采方法,提出了氧化钙粉末表面包覆改性、氧化钙微球、氧化钙羟基注入液、高压空气氧化钙粉末注入等核心技术工艺路径。     

珠江口盆地番禺低隆起-白云凹陷北坡干酪根热演化模拟与生烃

通过密封金管-高压釜体系对珠江口盆地番禺低隆起-白云凹陷北坡恩平组炭质泥岩的干酪根(PY),在24.1 MPa压力、20℃/hr(373.5~526℃)和2℃/h(343~489.2℃)两个升温速率条件下进行热模拟生烃实验,分析气态烃(C1 5)和液态烃(C6 14和C14+)的产率,以及沥青质和残余有机质碳同位素组成。同时与Green River页岩(GR)和Woodford泥岩(WF)的干酪根,分别代表典型的I型和II型干酪根进行对比研究。结果显示PY热演化产物中总油气量明显低于GR和WF干酪根,且气态烃(C1 5)最高产率是液态烃的1.5倍,揭示恩平组炭质泥岩主要以形成气态烃为主。在热演化过程中,有机质成熟度和母质类型是控制油气比的主要因素,气态烃和轻烃的产率比值主要受热演化成熟度的影响。干酪根残余有机质碳同位素和沥青质碳同位素在热演化过程中受有机质成熟度的影响较小,δ13C残余和δ13C沥青质可以间接反映原始母质的特征,为高演化烃源岩油气生成提供依据。     

基于压机热模拟实验的页岩孔隙演化特征

富有机质页岩微观孔隙结构是影响页岩油气富集的重要因素,但热演化过程中的孔隙结构变化特征不甚清楚,是当前领域研究的难点.用新疆三塘湖盆地中二叠统芦草沟组低成熟油页岩样品开展高温高压半封闭体系热模拟实验,对各温度阶段的样品进行抽提,利用低温吸附技术定量表征未抽提和抽提样品的孔隙结构,揭示低熟到过成熟页岩样品的孔隙演化特征.结果表明:低熟-成熟阶段,中、大孔量随热模拟温度上升而降低,微孔量先降低再升高,高压及滞留油/沥青对所有孔隙均有一定的抑制作用;高-过成熟阶段,孔含量明显上升,残留沥青中会产生微孔及中、大孔.在热模拟实验中温度、压力条件对孔隙结构具有重要影响,有机质演化产物与孔隙演化趋势紧密相关.      

页岩油地质评价实验测试技术研究进展

页岩油实验测试分析在页岩油地质评价中发挥着重要作用,目前页岩油储层矿物组成、有机质类型、丰度、物性以及岩石脆性等诸多方面的评价参数均需要通过实验测试来获取。本文评述了页岩油储层评价中烃源岩特性、储层储集性、含油性、可动性及可压性等各项实验测试技术研究现状和趋势,重点阐述了各项实验测试技术的目的及方法。页岩油烃源岩特性要综合有机质类型,丰度,成熟度,生物标志化合物,主量、微量和稀土元素等进行全面准确的评价;储集性与页岩矿物组成、孔隙、裂缝等储集空间分布特征密切相关,结合页岩含油饱和度、页岩油黏度、密度等评价页岩含油性和可动性;页岩可压性评价需综合考虑页岩的矿物组成、岩石力学特征参数等因素。同时探讨了页岩油储层地质评价实验测试技术未来发展方向,指出多种方法联合表征页岩油储层储集空间分布特征、不同赋存状态页岩油的分布特征、天然裂缝发育分析等是页岩油储层地质评价技术的关键攻关方向。