轻度微生物降解作用对原油中C_7轻烃的影响:以大宛齐油田为例

大宛齐油田全油样品的GC分析显示,部分样品经受了不同程度的微生物降解作用。对原油C7轻烃组成分析发现,随微生物降解程度的增加,链烷烃、环烷烃的相对丰度呈现规律性的变化。对不同支链烷烃而言,单甲基链烷烃比双甲基链烷烃和三甲基链烷烃优先降解,2,3-二甲基戊烷是C7支链烷烃中抗微生物降解能力最强的;2-甲基己烷比3-甲基己烷优先降解,甲基位于末端位置的比位于中间位置的异构体更易于被细菌攻击;烷基化程度和烷基化位置是影响微生物降解的两个主要因素。对于环烷烃,在较为强烈的微生物降解条件下,只剩下1,1-二甲基环戊烷,1,1-二甲基环戊烷是所有C7类烃中抗微生物降解能力最强的。随微生物降解程度的增加,Mango轻烃参数K1值减小、K2值增大,正庚烷值和异庚烷值减小,甲基环己烷指数增加,Halpern变化参数Tr2、Tr3、Tr4、Tr5均减小。     

渤中19-6潜山构造带凝析油中轻烃地球化学特征及意义

为了明确渤海湾盆地渤中19-6大气田的地化特征和成因,选取研究区潜山凝析气藏7个凝析油样品进行全油色谱分析,剖析其轻烃组成特征,探讨轻烃参数在该区的地质应用.结果表明:渤中19-6凝析油的Mango轻烃参数K₁和K₂值相对稳定,表明研究区原油成因类型基本一致.C₆~C₈组成中正构烷烃具显著优势,甲基环己烷指数平均为39%;庚烷值与异庚烷值,正庚烷/甲基环己烷（F）比值较高,反映它们较高成熟度;轻烃参数计算原油生成温度为125.8~128.1 ℃,其相对偏低,可能与取样过程中凝析油的相态变化有关;2-甲基戊烷/3-甲基戊烷,2-甲基己烷/3-甲基己烷比值高,K₂值低;凝析油正构烷烃摩尔浓度呈三段式分布,甲苯/正庚烷和原油蜡含量随深度而增加.结合饱和烃参数以及金刚烷参数揭示渤中19-6潜山油气为湖相腐泥Ⅱ₁型母质在高成熟阶段（Ro=1.05%~1.30%）的产物,气藏形成后发生一定程度分馏造成油气组分调整.      

煤成气轻烃地球化学特征及其影响因素——以四川盆地须家河组为例

轻烃在天然气中含量虽低,但因其含有丰富的地球化学信息,在天然气成因等研究方面引起了关注。作者以四川盆地须家河组煤成气和雷三段油型气为例,采用GC和GC-IR-MS技术对煤成气轻烃的地球化学分布特征及其影响因素进行了系统分析。煤成气C₇轻烃组成具有甲基环己烷分布优势,在甲基环己烷、正庚烷和二甲基环戊烷相对组成中,甲基环己烷含量最高,分布在48%~73%,平均为63.9%,煤成气轻烃单体烃碳同位素重,δ¹³C分布在-25.1‰~-20.0‰之间,大部分分布在-23.0‰~-21.0‰。轻烃的分布受到多种因素影响,天然气成熟度对轻烃中芳烃含量变化影响复杂,在成熟和高成熟阶段,天然气轻烃中芳烃含量低,成熟度对芳烃的含量影响较小,而在过成熟阶段,芳烃含量高,成熟度对芳烃含量影响大。通过凝析油和天然气轻烃组成对比,蒸发分馏作用对热演化参数Ctemp和庚烷值、甲苯/正庚烷等影响较大,但对成因类型参数如(2-MH+2,3-DMP)/C₇与(3-MH+2,4-DMP)/C₇,P2/C₇与N2/P3,正庚烷、甲基环己烷和二甲基环戊烷相对含量关系等影响小。天然气成因类型对轻烃Mango参数K1值、正庚烷、甲基环己烷和二甲基环戊烷相对含量关系以及轻烃单体烃碳同位素影响大,因此,可以利用这些参数进行天然气成因类型判识。     

松辽盆地南部浅层天然气地球化学特征及其成因分析

由于松辽盆地南部浅层天然气成因研究比较薄弱,通过采集伏龙泉地区泉头组天然气样品,对天然气组分、碳同位素、轻烃组分进行了分析。结果表明该地区天然气有油型气和生物降解气2种成因。第一类天然气甲烷碳同位素值在-35‰左右,甲烷及其同系物碳同位素呈正碳分布;甲基环己烷指数在20%左右、环己烷指数略高于10%,符合油型气的特征。由甲烷碳同位素计算的R₀值,以及轻烃中的庚烷值和异庚烷值均在高-过成熟的范围,因此是高成熟的油型气。第二类天然气甲烷碳同位素偏轻,丙烷碳同位素偏重;轻烃色谱图中以环烷烃为主峰,轻烃内组成中支链烷烃和环烷烃含量高,各项轻烃参数(甲基环己烷指数、庚烷值、K1值等)都在较大范围内波动,为生物降解气。这一研究对于今后该区天然气勘探与资源评价及其成藏机理研究具有重要意义。     

柴达木盆地原油地球化学特征及其源岩时代判识

在系统分析柴达木盆地北缘和西部各油田60余个原油样品轻烃、饱和烃和芳烃组成的基础上,全面揭示了两地区原油的标志性地球化学特征;并结合源岩分析资料,应用断代生物标志物建立了识别原油源岩时代的标志。研究结果表明,北缘各油田原油Mango轻烃参数K_1值波动在1.1上下,富含甲基环已烷和甲苯;正烷烃呈奇偶优势分布,姥鲛烷优势显著;反映侏罗系淡水湖沼相沉积有机质特征。西部原油K_1值大多在1.2以上,轻烃中富含异构支链化合物;正烷烃系列呈奇碳优势(C_(11)～C(17))和偶碳优势(C_(18)～C_(28))双重分布模式,强植烷优势;C_(28)甾烷相对含量高(>30％);脱羟基维生素E系列化合物丰富,5,7,8-三甲基-/8-甲基-MTTC比值大都低于10;表征古近系—新近系咸水湖相有机质性质。奥利烷和C_(26)降胆甾烷是区分侏罗系和古近系—新近系油源油的有效断代生物标志物。侏罗系原油无奥利烷,24-/(24-+27-)降胆甾烷比值小于0.25;古近系—新近系原油含有奥利烷,24-/(24-+27-)降胆甾烷比值高于0.6。     

塔里木盆地原油轻烃单体烃碳同位素组成特征

为探讨塔里木盆地原油类型和油源问题,运用色谱-同位素质谱分析技术,分析了该盆地塔中、塔北、塔东与库车地区的典型原油轻烃单体烃碳同位素组成。结果表明,不同结构轻烃化合物中,支链烷烃与环己烷系列比环戊烷系列更具明显的成因判识意义。2-甲基环戊烷2 mC_5、3-甲基环戊烷3 mC_5、3-甲基环己烷3 mC_6、环己烷CYC6与甲基环己烷mCYC_6等化合物的δ~(13)C在煤成油最高,δ~(13)C大于-21‰;湖相油次之,δ~(13)C位于-25‰~-22‰之间;再次之为寒武系-下奥陶统海相原油,δ~(13)C位于-27‰~-21‰之间,最轻的为上奥陶统海相原油,δ~(13)C小于-28‰。其碳同位素值可以较好的判别该盆地寒武系-下奥陶统海相油、上奥陶统海相油、湖相油与煤成油。优选的8个特征化合物碳同位素可以作为原油成因类型的划分标志,尤其是2-甲基环戊烷2 mC_5、3-甲基环戊烷3 mC_5、3-甲基环己烷3 mC_6、环己烷CYC6与甲基环己烷mCYC_6等化合物。特征轻烃化合物的碳同位素组成可成为不同成因原油的划分标志。     

实验室条件下微生物降解原油的地球化学特征研究

通过对胜利油田四个正常原油样品微生物作用前后的族组分及饱和烃色谱质谱分析,发现实验室条件下微生物对原油有明显的降解作用。微生物作用以后的原油族组分其饱和烃相对含量降低,饱/芳比也明显降低,而芳烃、非烃和沥青质的相对含量都不同程度的升高。通过饱和烃色谱-质谱分析,发现微生物作用以后原油正构烷烃被严重降解,姥/植(Pr/Ph)比值和∑C_21-/∑C₂₂₊比值都明显降低。微生物作用原油后能产生表面活性剂,造成了培养基表面张力的降低。     

突泉盆地突参1井原油中轻烃和金刚烷地球化学特征及油源启示

采用全烃气相色谱、全油气相色谱-质谱技术,研究了突泉盆地突参1井原油的轻烃和金刚烷类化合物特征,剖析其母质类型、沉积环境、成熟度等方面的信息及地质地球化学意义.突参1井原油Pr/Ph=3.17,姥鲛烷优势明显,指示为偏氧化的沉积环境;甲基环己烷指数MCH为46%,环己烷指数CH为25%,3,4DMD在二甲基金刚烷类化合物中占据一定的优势,其相对含量为48%,根据图版所示揭示其母质类型为Ⅱ₂-Ⅲ型;正庚烷指数（IH）为27.6%,异庚烷指数（Ⅱ）为0.33,甲基单金刚烷成熟度指数（IMA）为0.63,二甲基双金刚烷成熟度指数（IMD）为0.38,经公式计算Ro约为1.2%,属于成熟-高成熟阶段.结合前人研究资料,认为突参1井原油来自于中侏罗统万宝组煤系泥岩.     

东营凹陷烃源岩轻烃特征

以1-己烯和1-壬烯为内标物质,采用低沸点溶剂密封抽提色谱分析技术,对东营有效烃源岩的轻烃进行了定量分析,在准确获取C1～C15组分质量分数的同时又能得到有重要信息的轻烃参数.分析表明岩石中的轻烃与可溶有机质(轻烃 沥青"A")的质量分数比值平均可达14.59%,并随演化程度的增强而增大;链烷烃和环烷烃质量分数比值与成熟度有很好的线性关系,当链烷烃与环烷烃质量分数比值等于1～2时为低熟阶段,当链烷烃与环烷烃质量分数比值等于2～6时为成熟阶段;证实了2,4-二甲基戊烷与2,3-二甲基戊烷质量分数比值的对数是温度的函数,利用相应的计算公式可获取源岩经历的最高埋藏温度.     

在线富集-气相色谱法分析天然气中痕量轻烃

建立了高演化天然气在线富集-气相色谱分析方法,将干燥系数大于0.95的高演化天然气流经自行研制的富集反吹装置,痕量轻烃组分在富集管中冷冻液化并富集,对未液化的组分进行反吹,通过加热富集管使已液化的轻烃组分气化并进入色谱仪进行检测.分析结果表明,化合物的分析范围明显扩大,甲烷溶剂效应降低,达到对C10之前轻烃指纹进行分析的目的;对普光7井天然气样品进行3次重复性实验,所得甲基环己烷指数、正庚烷值、异庚烷值、Mango K1指数的实测最大重复性(r值)为0.22、0.23、0.02、0.00,分别小于国家标准要求的0.82、0.75、0.11、0.04,方法稳定可靠.通过本方法得到的轻烃参数可有效地应用于天然气成因类型、热演化程度探讨中.     

The effect of slight to minor biodegradation on C<Subscript>6</Subscript> to C<Subscript>7</Subscript> light hydrocarbons in crude oils: a case study from Dawanqi Oilfield in the Tarim Basin,NW China

Light hydrocarbons (LHs) are one of the main petroleum fractions in crude oils, and carry much information regarding the genetic origin and alteration of crude oils. But secondary alterations—especially biodegradation—have a significant effect on the composition of LHs in crude oils. Because most of the LHs affected in oils underwent only slight biodegradation (rank 1 on the biodegradation scale), the variation of LHs can be used to describe more the refined features of biodegradation. Here, 23 crude oils from the Dawanqi Oilfield in the Tarim Basin, NW China, eleven of which have been biodegraded to different extents, were analyzed in order to investigate the effect of slight to minor biodegradation on C₆–C₇ LHs. The study results showed that biodegradation resulted in the prior depletion of straight-chained alkanes, followed by branched alkanes. In slight and minor biodegraded oils, such biodegradation scale could not sufficiently affect C₆–C₇ cycloalkanes. For branched C₆–C₇ alkanes, generally, monomethylalkanes are biodegraded earlier than dimethylalkanes and trimethylalkanes, which indicates that branched alkanes are more resistant to biodegradation, with the increase of substituted methyl groups on parent rings. The degree of alkylation is one of the primary controlling factors on the biodegradation of C₆–C₇ LHs. There is a particular case: although 2,2,3-trimethylbutane has a relative higher alkylation degree, 2,2-dimethylpentane is more resistant to biodegradation than 2,2,3-trimethylbutane. 2,2-Dimethylpentane is the most resistant to biodegradation in branched C₆–C₇ alkanes. Furthermore, the 2-methylpentane/3-methylpentane and 2-methylhexane/3-methylhexane ratios decreased steadily with increasing biodegradation, which implies that isomers of bilateral methyl groups are more prone to bacterial attack relative to mid-chain isomers. The position of the alkyls on the carbon skeleton is also one of the critical factors controlling the rate of biodegradation. With increasing biodegradation, Mango’s LH parameters K1 values decrease and K2 values increase, the values of n-heptane and isoheptane decrease, and the indices of methylcyclohexane and cyclohexane increase. LH parameters should be applied cautiously for the biodegraded oils. Because biodegraded samples belong to slight or minor biodegraded oils, the values of n-heptane and isoheptane from Dawanqi Oilfield can better reflect and determine the “Biodegraded” zone. When the heptane value is 0–21 and the isoheptane value is 0–2.6, the crude oil in Dawanqi Oilfield is defined as the “Biodegraded” zone.     

Compositional and geochemical characteristics of light hydrocarbons for typical marine oils and typical coal-generated oils in China

Different types of crude oils have different light hydrocarbon compositional and geochemical characteristics. Based on the light hydrocarbon data from two kinds of oils, i.e., coal-generated oils and marine oils in China, light hydrocarbons in marine oils in the Tazhong area are generally relatively enriched in n-heptane, and coal-generated oils from the Turpan Basin are enriched in methylcyclohexane. The K1 values, reported by Mango （1987）, range from 0.97 to 1.19 in marine oils, basically consistent with what was reported by Mango on light hydrocarbons in terms of the majority of the crude oil data. But the K1 values of coal-generated oils are particularly high （1.35-1.66） and far greater than those of marine oils; heptane values in marine oils, ranging from 32.3% to 45.4%, and isoheptane values, ranging from 1.9 to 3.7, are respectively higher than those of coal-generated oils, indicating that the oils are in the high-maturity stage. In addition, expulsion temperatures of coal-generated oils from the Turpan Basin are obviously lower than those of marine oils from the Tazhong area.     

Deciphering biodegradation effects on light hydrocarbons in crude oils using their stable carbon isotopic composition: A case study from the Gullfaks oil field, offshore Norway

Compound-specific isotope analysis has become an important tool in environmental studies and is an especially powerful way to evaluate biodegradation of hydrocarbons. Here, carbon isotope ratios of light hydrocarbons were used to characterise in-reservoir biodegradation in the Gullfaks oil field, offshore Norway. Increasing biodegradation, as characterised, for example, by increasing concentration ratios of Pr/n-C₁₇ and Ph/n-C₁₈, and decreasing concentrations of individual light hydrocarbons were correlated to ¹³C-enrichment of the light hydrocarbons. The δ¹³C values of C₄ to C₉n-alkanes increase by 7-3‰ within the six oil samples from the Brent Group of the Gullfaks oil field, slight changes (1-3‰) being observed for several branched alkanes and benzene, whereas no change (<1‰) in δ¹³C occurs for cyclohexane, methylcyclohexane, and toluene. Application of the Rayleigh equation demonstrated high to fair correlation of concentration and isotope data of i- and n-pentane, n-hexane, and n-heptane, documenting that biodegradation in reservoirs can be described by the Rayleigh model. Using the appropriate isotope fractionation factor of n-hexane, derived from laboratory experiments, quantification of the loss of this petroleum constituent due to biodegradation is possible. Toluene, which is known to be highly susceptible to biodegradation, is not degraded within the Gullfaks oil field, implying that the local microbial community exhibits rather pronounced substrate specificities. The evaluation of combined molecular and isotopic data expands our understanding of the anaerobic degradation processes within this oil field and provides insight into the degradative capabilities of the microorganisms. Additionally, isotope analysis of unbiodegraded to slightly biodegraded crude oils from several oil fields surrounding Gullfaks illustrates the heterogeneity in isotopic composition of the light hydrocarbons due to source effects. This indicates that both source and also maturity effects have to be well constrained when using compound-specific isotope analysis for the assessment of biodegradation.     

高邮凹陷韦庄地区原油吡咯类含氮化合物运移分馏效应

高邮凹陷韦庄地区具有正常和轻微生物降解2类原油, 对油气运移方向一直存在争议.根据2类原油中含氮化合物浓度、屏蔽型含氮化合物的相对含量与反映原油生物降解的地化参数C₂₁-/C₂₂+、Pr/nC₁₇等nC₁₇物降解作用对该区原油中含氮化合物的相对含量及其分布影响不明显, 运移作用仍然是造成含氮化合物分馏的主要因素.自东向西、东北向西南方向, 韦X11井、韦6 - 2井、韦5 - 19井、韦8井原油中屏蔽型咔唑的相对含量依次增大, 分别为11.6 2 %, 10.6 6 %, 12.70 %, 13.88%;暴露型咔唑的相对含量则表现出相反的变化趋势, 分别为30.6 0 %, 2 8.5 6 %, 2 6.4 3%, 2 4.6 2 %.由此明确了本区油气自东、东北方向向西、西南方向注入, 深凹带和车逻鞍槽提供了主要油源.      

小太平山油砂油地球化学及生物降解特征

采用小太平山同一层位不同深度且连续的油砂样品,对油砂油的地球化学及生物降解特征进行分析。小太平山油砂油在生物降解作用下产生了丰富的25-降霍烷,常规藿烷和甾烷也发生了一系列变化。由于分子结构和稳定性不同,抗降解能力不同,C_(21)/C_(23)三环萜烷、伽马蜡烷/C_(30)藿烷、Ts/Tm、C_(30)重排藿烷/C_(30)藿烷值、αααC_(27)R/αααC_(29)R、C_(28)αααR/C_(29)αααR、C_(29)ααα20R/αββ20S、C_(29)ααα20R/αββ20R、C_(27)重排甾烷/(规则甾烷+重排甾烷)、常规藿烷异构体降解为25-降霍烷的比例,均反映出油砂油的生物降解程度随深度的增加而增大。小太平山油砂油随含水饱和度的增加降解程度增大,证实地层水有利于细菌类微生物的迁移、营养物质的传递,促进原油的生物降解及25-降霍烷的产生。     

生物降解原油地球化学研究新进展

生物降解作用是原油的一种重要的蚀变作用,对原油的物性和经济价值有着负面的影响。全球石油大多遭受过生物降解。生物降解作用对常见生物标志物的影响得以较好的描述,综述了近年来高分子量正构烷烃、三环萜烷、25 降藿烷生物降解的新进展。目前对生物降解作用的细节、发生机理尚不十分清楚,讨论了原油喜氧和厌氧降解机制,认为厌氧作用可能起主导作用,降解速率很慢。温度是控制生物降解作用的重要因素,储层温度大于80℃不会发生生物降解作用。生物降解原油多为混源油,介绍了研究生物降解原油的多期成藏方法。沥青质不易生物降解,其热解产物及钌离子催化氧化产物在生物降解原油对比、油源对比中具有重要的作用;最后指出了今后的发展方向。     

Demethylated hopanes in crude oils and their applications in petroleum geochemistry

Analyses of some Australian crude oils show that many contain varying concentrations of A/ B-ring demethylated hopanes. These range from C₂₆ to C₃₄ and have been identified from their retention times and mass spectral data as 17α(H)-25-norhopanes. Comparison of hopane and demethylated hopane concentrations and distributions in source-related, biodegraded oils suggests that demethylated hopanes are biotransformation products of the hopanes. Further, it appears that the process occurs at a late stage of biodegradation, after partial degradation of steranes has occurred. Demethylated hopanes are proposed as biomarkers for this stage of severe biodegradation. The presence of these compounds in apparently undegraded crude oils is thought to be due to the presence of biodegraded crude oil residues which have been dissolved by the undegraded crude oil during accumulation in the reservoir sands. The timing of hopane demethylation, relative to the degradation of other compounds, has been assessed and the progressive changes in crude oil composition with increasing extent of biodegradation have been identified. The use of demethylated hopanes as maturity parameters for severely biodegraded crude oils, and the applicability of established biomarker maturity parameters to such oils, are also discussed.     

Effects of Biodegradation on the Distribution of Alkylcarbazoles in Crude Oils

We have investigated the distributions of alkylcarbazoles in a series of crude oils with different biodegradation extents, in combination with biomarker parameters, stable carbon isotopic ratios and viscosities. The analyses showed that slight biodegradation has little effect on alkylcarbazoles. The concentrations of C₀-, C₁-, and C₂-carbazoles seem to display a slight decrease with biodegradation through the moderately biodegraded stage, and an abrupt decrease to the heavily biodegraded stage. The relative concentrations of C₀-, C₁-, and C₂-carbazoles do not show any apparent change in the non-heavily biodegraded stages, but through non-heavily biodegraded to heavily biodegraded stages, the percentages of C₀- and C₁-carbazoles decrease, and those of C₂-carbazoles increase significantly, which may indicate that C₂-carbazoles are more resistant to biodegradation than lower homologous species. As to C₂-carbazole isomers, the relative concentrations of the pyrrolic N-H-shielded, pyrrolic N−H partially shielded and pyrrolic N-H-exposed isomers do not show any obvious variation in the non-heavily biodegraded oil, but there is an abrupt change through the mid-biodegraded stage to the heavily biodegraded stage. This project was financially supported by the Youth Knowledge-Innovation Foundation of CNPC (No. 00Z1304).