塔里木盆地塔河油田原油地球化学特征的化学计量学分析及应用

塔里木盆地塔河油田由于存在多期次原油充注导致其成因至今无法得到很好地解释。应用地球化学手段对塔河油田原油地球化学特征进行综合研究,结果显示：塔河油田奥陶系原油沉积于海相沉积环境,处于成熟—过成熟阶段,正构烷烃分布较完整、具有UCM鼓包、普遍存在25?降藿烷、伽马蜡烷含量低,C₂₉藿烷丰度高、规则甾烷呈现C₂₉>C₂₇>C₂₈分布、规则甾烷αββ构型丰度高于ααα构型等特征,表明塔河油田原油遭受过较强程度的微生物降解作用,存在至少2个期次的原油充注。利用主成分分析（PCA）和层序聚类分析（HCA）方法对原油生物标志化合物指标进行分析,将塔河油田原油分为3类：I类原油具有三环萜烷/五环萜烷、Ts/17αC₃₀藿烷、重排甾烷/规则甾烷、C₃₁/C₃₂藿烷、C₂₉/C₃₀藿烷、C₂₄/C₂₃三环萜烷、C₂₀₊₁₉/C₂₃₊₂₄三环萜烷、Ts/Tm高,Ph/nC₁₈低,正构烷烃分布完整,呈现出多期充注特征,但主要表现出早期生物降解原油的特征,早期生物降解原油的贡献高于后期充注正常原油的贡献;II类原油的nC₂₁^-/nC₂₂⁺值最低,部分样品正构烷烃缺失,UCM鼓包明显,主要代表早期经历过强烈微生物降解的原油; III类原油nC₂₁^-/nC₂₂⁺、αβC₃₁?22S/（22S+22R）、C₂₄四环/（C₂₄四环+C₂₆三环）值最高,正构烷烃受热成熟度的影响最大,高碳数正构烷烃大量热裂解导致低碳数正构烷烃相对富集,代表混合原油但正常原油的贡献较大。     

渤海湾盆地青东凹陷古近系原油地球化学特征及油源分析

渤海湾盆地济阳坳陷青东凹陷存在常规原油和生物降解油。选取新参数β-胡萝卜烷/（2×C₂₉藿烷）、伽马蜡烷/（2×C₂₉藿烷）,三环萜烷系列参数（2×C₂₄四环萜烷）/（C₂₆三环萜烷）、（2×C₁₉）/（C₂₈+C₂₉）三环萜烷以及/菲,结合C₂₉ 4-甲基甾烷及碳同位素特征等,将该区原油划分为Ⅰ、Ⅱ、Ⅲ和Ⅳ等4类,烃源岩划分为A、B₁和B₂等3类。Ⅰ类原油来自青东凹陷中北部深洼的沙三下亚段成熟烃源岩,Ⅱ类原油来自凹陷南部沙四上亚段烃源岩,Ⅲ类原油来自中北部洼陷的沙四上亚段烃源岩,Ⅳ类原油来自青南洼陷沙四上亚段烃源岩,而青东8井原油应有青东凹陷南部烃源岩的贡献。      

原油中甾烷的生物降解模拟实验研究

通过喜氧细菌对原油的模拟生物降解实验,以及对模拟产物的饱和烃色谱—质谱分析,对原油饱和烃中规则甾烷和重排甾烷的降解作用进行了研究。研究结果显示,规则甾烷先于重排甾烷发生生物降解,甾烷降解由易到难的顺序为C₂7>C₂8>C₂9。在甾烷被大量降解前,20S/(20S+20R)(甾烷异构化作用)等生物标记化合物的成熟度指标基本无变化,但某些用于油源对比、母源和沉积环境研究的生物标记化合物参数可能会发生变化,如:规则甾烷/17α(H)-藿烷、C₂7-C₂8-C₂9甾烷、C₂7-C₂8-C₂9重排甾烷和重排甾烷/规则甾烷等。      

原油中C26－C28三芳甾烷相对含量计算方法及其应用

三芳甾烷（TAS）是规则甾烷芳构化产物,其中C₂₆-C₂₈三芳甾烷系列稳定分布于原油和烃源岩有机质中。在常规色谱-质谱分析得到的芳烃馏分（m/z231）质量色谱图上,由于C₂₆20R和C₂₇20STAS异构体共流出而不能确定3种不同碳数三芳甾烷的相对含量,无法建立类似于C₂₇-C₂₉规则甾烷的相对含量三角图,从而使三芳甾烷在油气地球化学中的应用受到限制。以塔里木盆地台盆区古生界代表性原油样品为例,建立了三芳甾烷相对含量三角图,并用北部湾盆地福山凹陷古近系原油进行了验证。结果表明:该区存在2种不同来源的原油,可以划分为2个不同的原油族群,而来自福山凹陷古近系的原油具有不同的C₂₆-C₂₈三芳甾烷组成特征,原油族群的划分也得到其他分子地球化学证据的支持。在高成熟的轻质油和凝析油中,规则甾烷系列由于浓度低而很难由常规的色谱-质谱分析技术进行检测和鉴定,三芳甾烷由于相对较高的热稳定性而稳定存在,因此可代替规则甾烷用于油-油对比和原油族群划分。      

南阳凹陷高蜡原油的地球化学特征

南阳凹陷原油为低密度、低粘度、低含硫和高凝固点的正常原油,高蜡-特高蜡也是南阳凹陷原油的主要特征。饱和烃含量高,饱和烃/芳香烃值大于3.0.C₂₇—C₂₉规则甾烷均呈“V”字型分布,C₂₉甾烷异构化作用较强,其比值为0.3~0.6.萜烷以五环三萜烷和长链三环萜烷为主,非藿烷系列(尤其是伽马蜡烷)含量相当丰富。个别样品伽马蜡烷指数高达1.3,为高盐度强还原环境。芳香烃组分以菲为优势组分,其次为萘系列,三芳甾烃在张店地区相对较低,且变化幅度较大。     

酒西坳陷原油地球化学特征与成熟度分类

酒西坳陷属于典型的勘探程度非常高的含油气坳陷,目前已发现的原油主要分布于青西凹陷和鸭儿峡-老君庙-石油沟构造带。这些原油绝大多数为正常密度和黏度的中-高蜡原油,只有少量为中-高蜡稠油,具有典型湖相原油的地球化学特征,全油碳同位素δ¹³C值为-32 ‰~-30 ‰,生物标志物组成总体相似,但分布特征存在一定差异,可以分为3类不同类型或成熟度原油。第1类为低成熟原油,甾烷以规则甾烷为主,没有重排甾烷;规则甾烷以ααα-20R甾烷为主,C₂₇、C₂₈、C₂₉甾烷呈不对称V型分布,C₂₉甾烷20S/（20S+20R）和ββ/（αα+ββ）值一般小于0.4;萜烷以五环萜烷为主,Ts、C₂₉Ts和C₃₀重排藿烷低,伽马蜡烷较高。第2类为中等成熟原油,Pr/Ph值一般小于1.0;甾烷也是以规则甾烷为主,没有重排甾烷,但ααα-20S和αββ甾烷明显高于第1类原油,C₂₉甾烷20S/（20S+20R）和ββ/（αα+ββ）值一般为0.40~0.55,C₂₇、C₂₈、C₂₉ ααα-20R甾烷呈不对称V型分布,C₂₇/C₂₉比值一般大于0.6;萜烷分布特征与第1类原油类似,Ts/Tm一般小于0.5;甾烷/萜烷比值基本大于1.0。第3类为高成熟原油,Pr/Ph值一般大于1.0;甾烷以规则甾烷为主,但重排甾烷明显且含量变化大,αββ甾烷明显高于ααα甾烷,C₂₉甾烷20S/（20S+20R）和ββ/（αα+ββ）值分别大于0.5和0.6,C₂₉甾烷含量明显高于C₂₇甾烷,C₂₇/C₂₉比值一般小于0.6;萜烷分布特征与前两类原油相似,但Ts、C₂₉Ts和C₃₀重排藿烷相对较高,Ts/Tm一般大于0.5,伽马蜡烷含量变化较大;甾烷/萜烷比值基本上小于1.0。     

塔中北斜坡西部原油类型及主力油源层

塔中北斜坡西部原油分为两类:Ⅰ类原油以相对低的三环萜烷/藿烷、孕凿烷/规则甾烷、重排甾烷/规则甾烷比值和高的Ts/Tm,C₃₀/C₃₁藿烷,C₂₈/C₂₉规则笛烷为特征;Ⅱ类原油与Ⅰ类原油的生物标志物特征相反.这表明北斜坡西部至少存在两个油源.油、源岩对比结果表明,Ⅰ类原油主要来源于寒武系烃源岩,Ⅱ类原油来源于中上奥陶统泥灰岩.     

涠洲油田油气地球化学特征及成因类型探讨

中石化涠西探区2015年获重大突破,涠西南D洼东部斜坡发现了涠洲油田。为揭示原油的成因和来源,此文采用地质地球化学技术,通过GC、GC-MS分析表明,原油中链烷烃组分以低碳数正构烷烃为主,平滑分布;甾萜烷异构化程度较高,富含重排甾烷,具丰富的C₃₀4-甲基甾烷以及低碳数甾烷,C₂₇、C₂₈、C₂₉规则甾烷呈"V"型或"L"型分布。油-油、油-源对比表明,涠洲油田原油与流沙港组优质的深湖-半深湖相烃源岩具有成因联系。原油成熟度参数C₂₉甾烷αββ/（αββ+ααα）、C₃₁升藿烷22 S/（S+R）等表明原油已达成熟阶段,利用甲基菲指数MPI1折算原油成熟度分布在0.79~0.97之间,原油成熟度与涠西南D洼流沙港组烃源岩热演化程度相当。综合以上分析认为,涠洲油田的原油表现为典型湖相特征,主要来源于涠西南D洼流沙港组烃源岩。     

塔中北坡SH9井区柯坪塔格组下段原油地球化学特征

塔中北坡SH9井区在柯坪塔格组下段首次发现了中—轻质黑油,具有低粘度、低含硫、低凝固点、高含蜡等特征。族组分中总烃含量、饱芳比均较大,碳同位素轻,小于-31‰。正构烷烃总体为单峰、前峰型分布,正构烷烃保存相对完整,但有轻微的“鼓包”（UCM峰）,具有轻微生物降解的特征;CPI值为1.04~1.05,Pr/Ph值为0.84~0.94,不具备奇偶优势,有明显的植烷优势。规则甾烷均呈“V”字形分布,C₂₈20R甾烷相对含量小于25%,C₂₉甾烷含量高于C₂₇甾烷,重排甾烷、升孕甾烷和孕甾烷的相对含量较高。三环萜烷系列的丰度高于藿烷系列,并在三环萜烷中表现为C₂₃三环萜烷的丰度优势,伽马蜡烷含量也较高。原油具有硫芴优势,三芳甲藻甾烷和甲藻甾烷欠发育;成熟度指标表征其为成熟油。认为该原油主要来源于中、上奥陶统烃源岩,中、下寒武统烃源岩贡献不明显。      

柴达木盆地西部七个泉与咸水泉油田原油地球化学特征对比研究

通过对取自七个泉油田和咸水泉油田原油样品中各类生物标志物的分布与组成特征的对比,发现七个泉油田原油中正构烷烃系列比较完整且丰度较高,而咸水泉油田原油中正构烷烃因轻微生物降解而被部分消耗,导致咸水泉油田原油的Pr/nC₁₇值和Ph/nC₁₈值明显高于七个泉油田原油。2个油田原油均呈现较强烈的植烷优势,七个泉油田原油的姥/植比更低,表明它们都来源于强还原环境下形成的烃源岩。在生物标志物分布与组成特征上,七个泉油田原油甾烷的C₂₇/C₂₉>1,而咸水泉[JP2]油田原油甾烷的C₂₇/C₂₉值均为0.8,意味着七个泉油田原油中浮游植物贡献高于咸水泉油田。咸水泉油田原油的C₂₉甾烷ααα20S/（ααα20S＋ααα20R）值和重排补身烷含量高于七个泉油田原油,暗示咸水泉油田原油成熟度比七个泉油田原油成熟度高。2个油田的长链藿烷序列均比较完整,伽马蜡烷含量也较高,对比长链藿烷和伽马蜡烷的丰度发现咸水泉油田原油的长链藿烷和伽马蜡烷丰度都比七个泉油田原油低,说明咸水泉油田原油形成的环境的盐度和还原性比七个泉油田原油弱。     

准噶尔盆地玛湖凹陷二叠系烃源岩三芳甾烷分布特征及油源对比

准噶尔盆地玛湖凹陷二叠系风城组、乌尔禾组和其他不同层系原油中普遍检测出三芳甾烷(TAS)和三芳甲藻甾烷系列。基于多口井的原油和14块代表性烃源岩样品的芳烃组分色谱-质谱资料,系统分析其TAS组成特征,并将其用于油源对比研究。结果表明：TAS分布特征可以有效区分准噶尔盆地玛湖凹陷二叠系风城组烃源岩和乌尔禾组烃源岩。风城组烃源岩中TAS具有C₂₆-20S含量低、C₂₇-20R含量高的分布特征,并且几乎不含有三芳甲藻甾烷;而乌尔禾组烃源岩中TAS具有相反的分布特征,即C₂₆-20S相对丰度较高,C₂₇-20R相对丰度较低,并且具有分布完整的三芳甲藻甾烷系列。玛湖凹陷不同层系原油TAS分布特征基本一致,主要表现为C₂₆-20S含量低,C₂₇-20R含量高,三芳甲藻甾烷含量低或者未检测出,与风城组烃源岩分布特征相似。应用C₂₆-20S/C₂₈-20S TAS与C₂₇-20R/C₂₈     

AN EXPERIMENTAL STUDY OF THE EFFECT OF PARAFFINIC SOLVENTS ON THE ONSET AND BULK PRECIPITATION OF ASPHALTENES

Asphaltene onset concentration and bulk deposition were measured for a typical live reservoir oil titrated with n-C₆H₁₄, n-C₅H₁₂, n-C₄H₁₀, C₃H₈, C₂H₆, CH₄ and CO₂ at 100° C (212 ° F) and 29.9 MPa (4340 psia). The concentration of titrant at asphaltene onset was observed to decrease approximately in a linear fashion with decreasing molecular weight of the paraffinic solvent; CH₄ did not induce any asphaltene precipitation. Bulk deposition experiments were performed using a solvent: oil volume ratio of 10:1; the results indicated that the weight percent of asphaltenes precipitated increased exponentially with decreasing molecular weight of the paraffinic solvents. More importantly, the asphaltene molecular weight showed a maximum for n-C₄H₁₀ precipitated asphaltenes. Possible explanations for this unusual result are presented.     

Evaluation of Effects of Selected Wax Inhibitors on Paraffin Deposition

Deposition from decane solutions of model paraffins such as n-C₂₄H₅₀ (C₂₄), and n-C₃₆H₇₄ (C₃₆), as well as a mixture of n-alkanes (C₂₁ to C₄₄) was examined with and without chemical wax deposition inhibitors. The device used to produce the deposits investigated was a “Cold Disk” Wax Deposition Apparatus (CoDWaD) capable of producing field like deposits with relatively small volumes of oil in minutes. It was found that most of commercial wax inhibitors tested could decrease the deposition of low molecular weight paraffins (C₃₄ and below), while having little effect on the wax deposition for high molecular weight paraffins (C₃₅-C₄₄). In many cases, although the total amount of wax formed on the cold plate was reduced, the absolute amount of deposition for high molecular wax was actually increased. Therefore, the net effect of many commercial inhibitors is to make even harder wax under the tests conditions studied here. One intriguing result was that the addition of an oleic imidazoline c rrosion inhibitor improved the performance of two wax inhibitors tested. It was also observed that there are subtle differences in inhibitor performance depending on whether the test solutions are binary mixtures, synthetic wax mixtures, or crude oil.     

GEOCHEMICAL SIGNIFICANCE OF FATTY ACIDS IN CRUDE OILS AND RELATED SOURCE ROCKS FROM EGYPT

The acid fraction of crude oils and related source rocks of different stratigraphic units from the Gulf of Suez and Western Desert, Egypt were analyzed by GC and GC/MS. Normal alkanoic acids (n-C₉-n-C₃₀) were the dominant series (with the predominance of even-carbon numbers maximizing at n-C₁₆, n-C₁₈ or n-C₂₂while iso- and anteiso- branched acids were minor constituents. All samples showed a preference of short chain acids (n-C₁₀-n-C₁₉ with respect to long chain acids (n-C₂₀+) typical of marine oils and source rocks. The n-alkanoic acids distribution suggests a predominant algal and/or bacterial contribution. The presence of high relative abundance of mono and di-unsaturated carboxylic acids in a number of samples point to recent microbial activity. Distributions of n-alkanoic acids in the range (C₁₂-C₂₂) show striking similarities with the n-alkane distributions, indicating that both series may, at least in part, be diagenetically related by decarboxylation of the acids. Dehydroabietic acid has been identified in only one sample from Balaim Marine source rock. This resin-derived compound has probably been transported as pollen to the marine environment.     

Evaluation of Effects of Selected Wax Inhibitors on Wax Appearance and Disappearance Temperatures

In this investigation, a light transmittance method was used to evaluate the wax appearance temperatures (WAT) and wax disappearance temperatures (WDT) of model paraffin compounds (n-C₂₄H₅₀ (C₂₄) and n-C₃₆H₇₄ (C₃₆)) in n-decane (C₁₀) solutions both with and without wax inhibitors. The change in WAT at different paraffin concentrations in the presence of an inhibitor behaves as though there is a constant amount of paraffin removed by the inhibitor. However, the amount of apparent paraffin reduction by an inhibitor (e.g. 160 g of C₂₄ by one gram of an inhibitor) indicates that the inhibition mechanism cannot easily be explained by a simple “sequestering” effect. Wax inhibitors that decrease the WAT tend to also increase the WDT. Most of the wax inhibitors tested at a dosage of 100 ppm did suppress the WAT of lower molecular weight paraffin (C₂₄) solutions, but had little or no effect for higher molecular weight paraffin (C₃₆) solutions. Side-chain length of polymethacrylate wax inhibitors is an important performance parameter. Of the three polymethacrylate wax inhibitors tested, the one with the longest alkyl side-chain (C₁₈) had the most effect on suppressing the WAT and increasing the WDT of the binary mixtures (n-C₁₀-n-C₂₄ solutions).     

一组有效区分渤中凹陷烃源岩的生物标志化合物参数

渤中凹陷是渤海湾盆地面积最大的二级构造单元，发育古近系沙河街组一段、沙河街组三段和东营组三段3套优质湖相烃源岩。准确识别东营组三段烃源岩贡献的原油，对于渤中凹陷油气勘探具有重要的理论和实践意义。根据烃源岩和原油芳烃馏分的色谱-质谱分析结果，提出了新的能够鉴别沙河街组三段和东营组三段烃源岩的生物标志化合物参数：C₂₇20R/C₂₈20R三芳甾烷和C₂₈20S/C₂₇20R三芳甾烷。东营组三段烃源岩的判识标准为C₂₇20R/C₂₈20R三芳甾烷>1.1，C₂₈20S/C₂₇20R三芳甾烷≤ 1.2；沙河街组三段烃源岩的判识标准为C₂₇20R/C₂₈20R三芳甾烷≤ 1.1，C₂₈20S/C₂₇20R三芳甾烷>1.2。据此，对渤中凹陷典型油田中原油的来源开展了判识，提出来自东营组三段烃源岩的原油具有近凹成藏的特点。     

南襄盆地泌阳凹陷西部稠油地化特征及意义

精细刻画稠油地球化学特征,对其油源对比、成因乃至开发都具有一定指导作用。南襄盆地泌阳凹陷西部地区原油均遭受了中等以上级别的生物降解,规则甾烷和藿烷受到不同程度破坏,使得一些反映原油成因、成熟度的常用指标严重失效。通过对该区12个稠油样品地球化学特征的精细分析和研究,发现饱和烃中的伽马蜡烷、Ts、Tm以及长链三环萜烷的抗降解能力高于规则甾烷和藿烷,能较好地反映该区稠油地球化学特征。油源对比表明,该区核三下段原油均来源于核三下段烃源岩,而核三上段原油除来源于核三上段烃源岩外,不同小层段都有核三下段源岩不同程度的贡献。结合芳烃组成特征和参数,可以清楚地将研究区稠油划分成两类,并显示他们可能具有不同的生物降解机制。