库车坳陷原油中重排藿烷类化合物的组成特征与成因探讨
发布时间：2018-08-02 15:26
【摘要】：重排藿烷类化合物是饱和烃生物标志化合物的重要组成部分,广泛分布于地质体中的烃源岩与原油中。近年来,有关高丰度重排藿烷类化合物的烃源岩和原油的研究成果屡见报道,但其来源与成因尚不清楚。所以探讨地质体中高含量重排藿烷类化合物的形成条件、主控因素、成因机理以及在石油地质中的应用,对油气勘探领域中,尤其是对一些叠合盆地油气勘探过程中急需解决的关键问题如油-源的精细对比、主力油源岩的准确厘定具有重要的意义。本文在广泛调研国内外文献资料以及塔里木盆地库车坳陷(大宛齐油田和大北油田)相关地质资料的基础上,系统采集了46个原油样品。通过色谱、色谱-质谱分析技术,系统地剖析原油地球化学特征及其分布规律,结合原油中不同丰度的重排藿烷类化合物进行一系列的对比研究。刻画了不同丰度重排藿烷类化合物的原油在生标组合上的差异及其组成特征,探讨了沉积环境、生物来源以及成熟度对重排藿烷类化合物形成的影响。通过样品分析、资料处理以及地质-地球化学综合研究,主要取得了以下主要认识：1、塔里木盆地库车坳陷的46个原油样品以轻质油和凝析油为主。颜色从无色到深棕色。总体上原油性质具有6低特征：低密度、低粘度、低含硫量、低含蜡量、低胶质-沥青质、低凝固点的特点。全烃色谱面貌表现为大部分原油中正构烷烃分布完整,有苯系物与甲基环己烷的存在,少数原油样品受到不同程度次生蚀变作用的影响。2、原油C7轻烃系列组成总体上甲基环己烷(MCyC6)的相对百分含量占优势；规则甾烷C27、C28、C29主要呈不对称“V”型分布,且以C29甾烷为优势；芳烃化合物中以萘系列化合物为主,并检测到并检测到荧蒽、苯并[a]蒽和芘等化合物,说明有机质来源以陆源输入为主。原油饱和烃Pr/Ph主要介于1.2-3.0之间,伽马蜡烷／C30藿烷比值介于0.18-0.28,指示出淡水-微咸水条件下的弱氧化-弱还原环境。MPI-1、MPR、F1、F2的成熟度参数的研究均表明塔里木盆地库车坳陷原油处于成熟阶段,且成熟度差异不大。原油成因类型分为两种：第一类原油具有伽马蜡烷优势,重排甾烷、重排藿烷丰度较低；第二类原油伽马蜡烷的丰度相对较低,重排甾烷、重排藿烷十分发育。3、原油通过GC-MS分析检测出17a(H)-重排藿烷系列、18α[(H)-新藿烷系列以及早洗脱重排藿烷系列三个重排藿烷系列化合物。以C30重排藿烷/C30藿烷(C30*/C30H)比值为标准将重排藿烷类化合物的相对丰度划分为三个等级：C30*/C30H1.0时为异常高丰度重排藿烷(27个原油样品),C30*/C30H=0.2～1.0时为高丰度重排藿烷类(16个原油样品),C30*/C30H0.2时为低丰度重排藿烷(3个原油样品)。原油样品中重排藿烷类化合物之间的关系表明具有相似碳骨架结构的重排藿烷类化合物间相关性相对较好,而具有不同碳骨架的重排藿烷类化合物之间相关性与前者相比略微差之。说明重排藿烷类化合物中相同系列化合物具有相同演化路径与形成机制,而重排藿烷类化合物不同系列化合物形成机理可能有所差别。4、原油中重排藿烷类化合物与生标组合之间的关系：原油样品中伽马蜡烷比值(G/C30藿烷)的分布介于0.1-0.29之间,平均值为0.16。重排藿烷类化合物相对丰度与Pr/Ph、G/C30H三者之间呈现一定的相关性,显示出沉积环境可能对重排藿烷类化合物的相对丰度有一定的影响。原油中C24四环萜烷/C23三环萜烷(C24Te/C23TT)介于0.26-1.79之间,平均值为1.28；C24四环萜烷/C26三环萜烷(C24Te/C26TT)介于0.67-4.5之间,平均值为2.9。不同系列的重排藿烷类化合物与C24Te/C23TT、C24Te/C26TT均存在正相关关系,反映了C24四环萜烷与重排藿烷类化合物的形成可能存在某种程度的联系。原油中C27重排甾烷/C27规则甾烷比值分布在0.21-1.8之间,均值为0.89；C29重排甾烷/C29规则甾烷比值分布在0.18-0.65之间,均值为0.5。重排藿烷类化合物与重排甾烷参数之间表现出良好的正相关关系,揭示了重排甾烷可能与重排藿烷类化合物的形成机理相类似。5、原油中重排藿烷类化合物与芳烃化合物之间的关系：原油中二环芳烃和三环芳烃(低环芳烃)在低丰度重排藿烷类化合物的原油中相对百分含量较低,分布在94.66%～98.95%之间,平均值为96.84%,在高丰度和异常高丰度重排藿烷类化合物的原油中相对百分含量较高,平均达到了98.37%、98.55%。四环和五环芳烃(多环芳烃)则在高-异常高丰度重排藿烷类化合物的原油中相对百分含量较低,在低丰度重排藿烷原油中含量相对较高。重排藿烷类化合物有着随低环芳烃相对含量增大而增高、随多环芳烃相对含量降低而增高的趋势。由此可见,重排藿烷类化合物与二环芳烃和三环芳烃有着较为相似的形成条件和母质来源。原油三芴系列化合物中总体上以氧芴(OF)为主,其相对百分含量在22.95%-74.69%之间,平均为55.17%；其次是硫芴(SF)的相对含量平均为23.97%。原油样品中重排藿烷类化合物相对丰度与OF/(F+OF)之间存在正相关趋势。表明二者具有相似的沉积环境。6、原油中重排藿烷类化合物与次生作用之间的关系：主要是运移分馏作用对重排藿烷类化合物的影响。原油中烷基萘系列化合物中随多烷基萘丰度的降低,萘或甲基萘丰度是明显增加；菲系列化合物中随着多烷基菲相对丰度的降低,甲基菲和不带烷基侧链的菲的丰度增加。由于原油的成熟度差异较小,且微生物的轻度降解作用对芳烃组成的影响不大,因而这种分布特点很可能与原油的运移分馏作用有关。因此选取抗生物降解能力较强的金刚烷类化合物相关比值作为衡量原油运移分馏作用大小的参数,不同重排藿烷类化合物与1-甲基金刚烷／1-乙基金刚烷(1M-AD/1Et-AD)、1-甲基金刚烷／4-甲基双金刚烷(1M-AD/4-MDD)比值表现出一定相关性。表明运移分馏作用会对重排藿烷类化合物相对丰度的产生一定的影响。7、通过上述综合研究成果揭示,塔里木盆地库车坳陷原油中重排藿烷类化合物的相对丰度主要受控于沉积环境和生物来源。在弱氧化-弱还原环境中,水体盐度较低,陆源高等植物的贡献越大越有利于重排藿烷类化合物的形成。运移分馏作用对重排藿烷类化合物相对丰度的有一定影响,但不是主控因素；此外,本论文原油的成熟度相似,原油中重排藿烷类化合物的相对丰度与成熟度参数相关性没有很好的对应关系。
[Abstract]:Rearranged Epimedium is an important component of the biomarker of saturated hydrocarbon, which is widely distributed in source rocks and crude oil in geological bodies. In recent years, the research results of source rock and crude oil of high abundance reader compounds have been reported, but the source and cause are not clear. Therefore, the high content of the geological bodies is discussed. The formation conditions, main controlling factors, genetic mechanism and application in petroleum geology are important for the key problems of oil and gas exploration, such as the fine contrast of oil source in the oil and gas exploration of some superimposed basins, and the accurate determination of the main source rocks is of great significance. This paper is widely investigated in this paper. On the basis of relevant geological data from the domestic and foreign literature and the Kuche depression of the Tarim Basin (DA Wan Qi oilfield and daybei oilfield), 46 crude oil samples were collected systematically. The geochemical characteristics and distribution rules of crude oil were systematically analyzed by chromatography and chromatography-mass spectrometry. A series of comparative studies were carried out. The differences and composition characteristics of crude oil in the biological standard combinations were depicted. The effects of depositional environment, biological sources and maturity on the formation of rearrangement of rearranged plants were discussed. The following main understandings should be obtained: 1, 46 crude oil samples in the Kuche depression of Tarim Basin are mainly light oil and condensate oil. Color from colorless to dark brown. In general, the properties of crude oil have 6 low characteristics: low density, low viscosity, low sulfur content, low wax content, low glial asphaltene and low solidification point. All hydrocarbon chromatographic features are large. The distribution of n-alkanes in some crude oils is complete, with the presence of benzene and methyl cyclohexane, and some of the crude oil samples are affected by the secondary alteration of different degrees.2, and the relative percentage of methyl cyclohexane (MCyC6) is dominant in the C7 light hydrocarbon series of crude oil, and the C27, C28 and C29 of regular steranes are mainly asymmetric "V" type distribution. C29 sterane is dominant; naphthalene series compounds are the main compounds in aromatics, and fluoranthene, benzo, [a] anthracene and pyrene are detected and detected. It shows that the source of organic matter is mainly by land source. The crude oil saturated hydrocarbon Pr/Ph is between 1.2-3.0 and the ratio of gamma paraffane / C30 is 0.18-0.28, indicating the condition of fresh water and brackish water. The study on the maturity parameters of.MPI-1, MPR, F1 and F2 in the weak oxidation and weak reduction environment all indicate that the crude oil in Kuche depression in Tarim Basin is in the mature stage, and the difference of maturity is small. The origin type of the crude oil is divided into two kinds: the first kind of crude oil has the advantage of gamma paraffane, rearrangement sterane, the abundances of rearrangement of the rearrangement of the crude oil, the second kind of crude oil gamma wax The abundance of alkanes is relatively low, rearrangement of sterane, rearrangement of the rearrangement of.3, and the detection of 17a (H) - rearrangement Epimedium series by GC-MS, 18 alpha [(H) - Epimedium series and early eluate rearrangement rearrangement series of three rearrangement anadytine series. The rearrangement of the rearrangement of the rearrangement of the rearrangement of the rearrangement of the /C30 and the C30*/C30H) The relative abundance is divided into three grades: the abnormal high abundance rearrangement Epimedium (27 crude oil samples) at C30*/C30H1.0, the high abundance rearrangement Epimedium type (16 crude oil samples) and the low abundance rearrangement Epimedium (3 crude oil samples) at the time of C30*/C30H=0.2 to 1. The relationship between the rearrangement rearrangement of the crude oil samples shows that the relationship between the rearrangement and the rearrangement of the crude oil samples shows the phase. The correlation of the rearrangement reschedule like compounds with carbon skeleton is relatively good, but the correlation between the rearrangement reschedule compounds with different carbon skeletons is slightly worse than that of the former. It shows that the same series of compounds in the rearrangement reschedule compounds have the same evolutionary path and formation mechanism, and the rearrangement of the rearrangement of the rearrangement of the compound is different. The formation mechanism of the compound may be different.4, the relationship between the rearrangement of the crude oil in the crude oil and the biological standard combination: the distribution of the gamma paraffane ratio (G/C30) in the crude oil samples is between 0.1-0.29, and the mean value is that the relative abundance of the 0.16. rearrangement anadine compounds with Pr/Ph and G/C30H three shows a certain correlation. The sedimentary environment may have a certain influence on the relative abundance of rearranged padeanes. C24 tetracycline /C23 triterpene (C24Te/C23TT) in crude oil is between 0.26-1.79 and 1.28; C24 tetracyclic terpene /C26 triterpenane (C24Te/C26TT) is between 0.67-4.5, and the average value is 2.9. different series of rearrangement and C24. There is a positive correlation between Te/C23TT and C24Te/C26TT, which reflects the possible relationship between the C24 tetracycline and the rearrangement of the rearrangement of the compound. The /C27 regular sterane ratio of the C27 rearrangement sterane in the crude oil is between 0.21-1.8, with a mean of 0.89; the C29 rearrangement sterane /C29 gauge is distributed between 0.18-0.65 and 0.5. There is a good positive correlation between rearrangement and rearrangement of sterane parameters, which reveals that rearrangement sterane may be similar to.5, and the relationship between rearrangement reschedule and aromatics in crude oil: low abundance of PAH and arene (low cyclic aromatic hydrocarbons) in crude oil The relative percentage of the crude oil in the rearrangement of the crude oil is low, between 94.66% and 98.95%, with an average of 96.84%. The relatively high percentage of the crude oil in the crude oil of high abundance and abnormally high abundance of rearranged oil is 98.37%, the 98.55%. four ring and the five ring aromatic hydrocarbons (polycyclic aromatic hydrocarbons) are in high abnormally high abundance rearrangement. The relative content of the crude oil in the crude oil is relatively low, and the content of the crude oil in the low abundance rearrangement oil is relatively high. The rearrangement of the rearrangement compound increases with the increase of the relative content of the low cyclic aromatic hydrocarbons and increases with the decrease of the relative content of polycyclic aromatic hydrocarbons. There are relatively similar forming conditions and parent material sources. The three fluorene Series in crude oil are mainly composed of fluorene (OF), with a relative percentage of 55.17%, and the relative content of sulfur fluorene (SF) is the average of the relative abundance between the rearrangement and OF/ (F+OF) of the 23.97%. crude oil samples. The relationship between the two has a similar sedimentary environment.6, and the relationship between the rearrangement and secondary effects of the rearrangement of the crude oil is mainly the effect of the migration and fractionation on the rearrangement of the rearrangement compound. The abundances of alkyl naphthalene in the naphthalene series in the crude oil are decreased with the abundance of poly alkyl naphthalene, and the abundance of naphthalene or methylnaphthalene is obviously increased; As the relative abundance of do Kifi decreased, the abundance of phenanthrene in methyl phenanthrene and non alkyl side chains increased. Due to the small difference in maturity of crude oil, and the slight degradation of microbes had little effect on the composition of aromatics, this distribution was likely to be related to the migration and fractionation of the original oil. The relative ratio of adamantane compounds with strong degrading ability is used as a parameter to measure the size of crude oil migration and fractionation, and the ratio of different rearranged alanine compounds with 1- methyladamantane / 1- ethyl adamantane (1M-AD/1Et-AD), 1- methyladamantane / 4- methylene dimethyladamantane (1M-AD/4-MDD) has a certain correlation. The relative abundances of the rearrangement of the rearrangement of the compound were affected by.7. Through the comprehensive study, the relative abundance of the rearrangement of the oil in the Kuche depression of the Tarim Basin was mainly controlled by the sedimentary environment and the biological source. In the weak oxidation weak reduction ring, the salinity of the water body was low and the tribute of the high terrestrial plants was given. The migration and fractionation has a certain effect on the relative abundance of the rearrangement of the rearrangement of the rearrangement, but not the main control factor. In addition, the maturity of the crude oil is similar, and the relative abundance of the rearrangement of the rearrangement of the crude oil in the crude oil has no good correlation with the correlation of maturity parameters.
【学位授予单位】：长江大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：P618.13
本文编号：2159869
[Abstract]:Rearranged Epimedium is an important component of the biomarker of saturated hydrocarbon, which is widely distributed in source rocks and crude oil in geological bodies. In recent years, the research results of source rock and crude oil of high abundance reader compounds have been reported, but the source and cause are not clear. Therefore, the high content of the geological bodies is discussed. The formation conditions, main controlling factors, genetic mechanism and application in petroleum geology are important for the key problems of oil and gas exploration, such as the fine contrast of oil source in the oil and gas exploration of some superimposed basins, and the accurate determination of the main source rocks is of great significance. This paper is widely investigated in this paper. On the basis of relevant geological data from the domestic and foreign literature and the Kuche depression of the Tarim Basin (DA Wan Qi oilfield and daybei oilfield), 46 crude oil samples were collected systematically. The geochemical characteristics and distribution rules of crude oil were systematically analyzed by chromatography and chromatography-mass spectrometry. A series of comparative studies were carried out. The differences and composition characteristics of crude oil in the biological standard combinations were depicted. The effects of depositional environment, biological sources and maturity on the formation of rearrangement of rearranged plants were discussed. The following main understandings should be obtained: 1, 46 crude oil samples in the Kuche depression of Tarim Basin are mainly light oil and condensate oil. Color from colorless to dark brown. In general, the properties of crude oil have 6 low characteristics: low density, low viscosity, low sulfur content, low wax content, low glial asphaltene and low solidification point. All hydrocarbon chromatographic features are large. The distribution of n-alkanes in some crude oils is complete, with the presence of benzene and methyl cyclohexane, and some of the crude oil samples are affected by the secondary alteration of different degrees.2, and the relative percentage of methyl cyclohexane (MCyC6) is dominant in the C7 light hydrocarbon series of crude oil, and the C27, C28 and C29 of regular steranes are mainly asymmetric "V" type distribution. C29 sterane is dominant; naphthalene series compounds are the main compounds in aromatics, and fluoranthene, benzo, [a] anthracene and pyrene are detected and detected. It shows that the source of organic matter is mainly by land source. The crude oil saturated hydrocarbon Pr/Ph is between 1.2-3.0 and the ratio of gamma paraffane / C30 is 0.18-0.28, indicating the condition of fresh water and brackish water. The study on the maturity parameters of.MPI-1, MPR, F1 and F2 in the weak oxidation and weak reduction environment all indicate that the crude oil in Kuche depression in Tarim Basin is in the mature stage, and the difference of maturity is small. The origin type of the crude oil is divided into two kinds: the first kind of crude oil has the advantage of gamma paraffane, rearrangement sterane, the abundances of rearrangement of the rearrangement of the crude oil, the second kind of crude oil gamma wax The abundance of alkanes is relatively low, rearrangement of sterane, rearrangement of the rearrangement of.3, and the detection of 17a (H) - rearrangement Epimedium series by GC-MS, 18 alpha [(H) - Epimedium series and early eluate rearrangement rearrangement series of three rearrangement anadytine series. The rearrangement of the rearrangement of the rearrangement of the rearrangement of the rearrangement of the /C30 and the C30*/C30H) The relative abundance is divided into three grades: the abnormal high abundance rearrangement Epimedium (27 crude oil samples) at C30*/C30H1.0, the high abundance rearrangement Epimedium type (16 crude oil samples) and the low abundance rearrangement Epimedium (3 crude oil samples) at the time of C30*/C30H=0.2 to 1. The relationship between the rearrangement rearrangement of the crude oil samples shows that the relationship between the rearrangement and the rearrangement of the crude oil samples shows the phase. The correlation of the rearrangement reschedule like compounds with carbon skeleton is relatively good, but the correlation between the rearrangement reschedule compounds with different carbon skeletons is slightly worse than that of the former. It shows that the same series of compounds in the rearrangement reschedule compounds have the same evolutionary path and formation mechanism, and the rearrangement of the rearrangement of the rearrangement of the compound is different. The formation mechanism of the compound may be different.4, the relationship between the rearrangement of the crude oil in the crude oil and the biological standard combination: the distribution of the gamma paraffane ratio (G/C30) in the crude oil samples is between 0.1-0.29, and the mean value is that the relative abundance of the 0.16. rearrangement anadine compounds with Pr/Ph and G/C30H three shows a certain correlation. The sedimentary environment may have a certain influence on the relative abundance of rearranged padeanes. C24 tetracycline /C23 triterpene (C24Te/C23TT) in crude oil is between 0.26-1.79 and 1.28; C24 tetracyclic terpene /C26 triterpenane (C24Te/C26TT) is between 0.67-4.5, and the average value is 2.9. different series of rearrangement and C24. There is a positive correlation between Te/C23TT and C24Te/C26TT, which reflects the possible relationship between the C24 tetracycline and the rearrangement of the rearrangement of the compound. The /C27 regular sterane ratio of the C27 rearrangement sterane in the crude oil is between 0.21-1.8, with a mean of 0.89; the C29 rearrangement sterane /C29 gauge is distributed between 0.18-0.65 and 0.5. There is a good positive correlation between rearrangement and rearrangement of sterane parameters, which reveals that rearrangement sterane may be similar to.5, and the relationship between rearrangement reschedule and aromatics in crude oil: low abundance of PAH and arene (low cyclic aromatic hydrocarbons) in crude oil The relative percentage of the crude oil in the rearrangement of the crude oil is low, between 94.66% and 98.95%, with an average of 96.84%. The relatively high percentage of the crude oil in the crude oil of high abundance and abnormally high abundance of rearranged oil is 98.37%, the 98.55%. four ring and the five ring aromatic hydrocarbons (polycyclic aromatic hydrocarbons) are in high abnormally high abundance rearrangement. The relative content of the crude oil in the crude oil is relatively low, and the content of the crude oil in the low abundance rearrangement oil is relatively high. The rearrangement of the rearrangement compound increases with the increase of the relative content of the low cyclic aromatic hydrocarbons and increases with the decrease of the relative content of polycyclic aromatic hydrocarbons. There are relatively similar forming conditions and parent material sources. The three fluorene Series in crude oil are mainly composed of fluorene (OF), with a relative percentage of 55.17%, and the relative content of sulfur fluorene (SF) is the average of the relative abundance between the rearrangement and OF/ (F+OF) of the 23.97%. crude oil samples. The relationship between the two has a similar sedimentary environment.6, and the relationship between the rearrangement and secondary effects of the rearrangement of the crude oil is mainly the effect of the migration and fractionation on the rearrangement of the rearrangement compound. The abundances of alkyl naphthalene in the naphthalene series in the crude oil are decreased with the abundance of poly alkyl naphthalene, and the abundance of naphthalene or methylnaphthalene is obviously increased; As the relative abundance of do Kifi decreased, the abundance of phenanthrene in methyl phenanthrene and non alkyl side chains increased. Due to the small difference in maturity of crude oil, and the slight degradation of microbes had little effect on the composition of aromatics, this distribution was likely to be related to the migration and fractionation of the original oil. The relative ratio of adamantane compounds with strong degrading ability is used as a parameter to measure the size of crude oil migration and fractionation, and the ratio of different rearranged alanine compounds with 1- methyladamantane / 1- ethyl adamantane (1M-AD/1Et-AD), 1- methyladamantane / 4- methylene dimethyladamantane (1M-AD/4-MDD) has a certain correlation. The relative abundances of the rearrangement of the rearrangement of the compound were affected by.7. Through the comprehensive study, the relative abundance of the rearrangement of the oil in the Kuche depression of the Tarim Basin was mainly controlled by the sedimentary environment and the biological source. In the weak oxidation weak reduction ring, the salinity of the water body was low and the tribute of the high terrestrial plants was given. The migration and fractionation has a certain effect on the relative abundance of the rearrangement of the rearrangement of the rearrangement, but not the main control factor. In addition, the maturity of the crude oil is similar, and the relative abundance of the rearrangement of the rearrangement of the crude oil in the crude oil has no good correlation with the correlation of maturity parameters.
【学位授予单位】：长江大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：P618.13
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