原油热模拟实验中重排藿烷类变化特征及其意义

通过对TZ62井原油进行热模拟实验,探讨热演化程度对原油中重排藿烷类化合物形成分布的影响及其地球化学意义。实验发现：在400～500 ℃阶段,随着热演化程度的增加,原油中高碳数微晶蜡类长链化合物热裂解和原油中的沥青质热降解作用对重排藿烷的形成具有贡献作用。在500～550 ℃对应的原油裂解高峰阶段,藿烷类化合物浓度明显降低,且17α(H)-藿烷比重排藿烷类化合物具有更快的热裂解速率。在温度为550～600 ℃阶段,较高的热演化程度对17α(H)-藿烷甲基重排作用形成重排藿烷具有贡献作用。重排藿烷参数(17α(H)-重排藿烷/17α(H)-藿烷、Ts/Tm)在400～500 ℃变化较弱,几乎不受热演化程度的影响;在500～550 ℃的原油裂解高峰阶段,逐渐增大;在550～600 ℃发生反转,逐渐减小。重排藿烷参数可作为高成熟阶段原油成熟度判识的有效参数,其有效应用范围是生油窗晚期至原油裂解高峰期。     

De-A-steroids in immature marine shales

Three series of de-A-diasterenes have been observed in a variety of immature marine shales. Two of them have been identified by comparison with authentic standards and the structures of the third assigned by extrapolation. The greater complexity in the number of series compared with diasterenes indicates that the ring A degradation occurred to differing extents. The rate of C-20 diagenetic isomerisation in the de-A-diasterenes proceeds at a similar rate to that in diasterenes. Two series of B-ring monoaromatic de-A-steroid hydrocarbons have also been found. Comparison with the B-ring monoaromatic anthrasteroids indicates that the de-A-compounds are 14α(H) and 14β(H) isomers. Diagenetic isomerisation of the 14α(H) isomers to the more stable 14β(H) isomers occurs at a rate similar to that in the B-ring monoaromatic anthrasteroid series.     

冀中凹陷文安油田双环倍半萜的分布及其意义

基于全油气相色谱/质谱联用定量分析技术,分析了冀中凹陷文安油田原油中双环倍半萜在空间分布上的非均质性特征及其变化规律,并讨论了其非均质性特征的地质-地球化学意义。结果表明：微生物的降解作用对双环倍半萜的影响并不明显,文安油田原油含有丰富的双环倍半萜;文安油田原油中双环倍半萜的总体分布特征是C14倍半萜化合物相对丰度最小,C15倍半萜化合物相对丰度居中,C16倍半萜化合物相对丰度最高;文安油田南区与北区原油存在明显非均质性;重排补身烷与8β（H）-补身烷、C30重排藿烷与C30藿烷、C27重排甾烷与C27甾烷的相对丰度比值具有显著相关性,反映重排补身烷的形成机理与重排甾烷、重排藿烷的形成具有相似性;原油分子组成上的非均质性预示着文安油田原油可能存在两种不同的成因类型,文安油田南区和北区可能存在着2个油气富集体系。     

柯克亚油田原油地球化学特征和油源研究

应用GC/MS、GC/MS/MS分析技术,剖析了塔西南地区侏罗系和二叠系两套烃源岩生物标志物组合特征,建立了区分的指标体系,即二叠系源岩重排藿烷、C30-未知萜烷含量丰富,侏罗系源岩重排藿烷含量较低,但检测到二萜类化合物,而在二叠系源岩中未检测到该类化合物。柯克亚原油重排藿烷、C30-未知萜烷发育。精细油-岩对比结果表明,柯克亚原油主要来源于二叠系烃源岩,同时原油中检测出微量的二萜类化合物,说明侏罗系烃源岩也有一定的贡献。     

Relative stabilities of sedimentary rearranged sterenes as calculated by molecular mechanics: a key to unravel further steroid diagenesis

Molecular mechanics calculations of rearranged cholestenes revealed that diacholest-13(17)-enes with 10α stereochemistry are more stable than their 10β counterparts and that a partly rearranged sterene with a Δ⁸ double bond and 10β, 14β stereochemistry (compound 7) is relatively stable at thermodynamic equilibrium. The calculated data are in good agreement with sedimentary and experimental data and thus reinforce recent propositions for early-stage diagenesis of steroids.     

利用芳烃参数研究煤系烃源岩中重排藿烷成因

研究发现鄂尔多斯盆地部分地区上古生界煤系烃源岩存在较高丰度的17α(H)-重排藿烷和早洗脱重排藿烷,在对重排藿烷分布、组成特征及生标组成特征研究的基础上,应用芳烃参数对高丰度重排藿烷的成因进行了探讨。饱和烃生物标志物组成特征显示,高重排藿烷与陆源高等植物生源关系密切,主要在弱氧化沉积环境下演化形成。具有高-异常高丰度17α(H)-重排藿烷和早洗脱重排藿烷(C₃₀*/C₃₀H>0.2、C₃₀E/C₃₀H>0.1)的烃源岩二环+三环芳烃相对含量一般大于50%,四环、五环芳烃含量相对较低,普遍低于35%,未见芳香甾萜类,研究认为其生源主要为陆生高等植物;甲基菲指数MPI₁、MPI₂和甲基菲比值F1研究结果显示,Pr/Ph>1的弱氧化环境烃源岩17α(H)-重排藿烷和早洗脱重排藿烷在进入成熟阶段后开始大量形成,并随成熟度升高而增大;Pr/Ph<1还原环境下的烃源岩重排藿烷丰度相对较低,但在进入成熟阶段后仍有随成熟度升高而增大的趋势;三芴系列化合物参数表明,沉积环境的弱氧化性质对17α(H)-重排藿烷和早洗脱重排藿烷的形成有较大的影响,沼泽相沉积环境最有利于重排藿烷的形成。     

Strenes and triterpenes in brown coals

The method of gas chromatography-mass spectrometry was used to identify rearranged 24-methylcholestenes, 24-ethylcholestenes and isohopene in brown coals. Possible routes and sources of formation of these hydrocarbons in nature are discussed. Mass spectra both of original hydrocarbons and of their saturated analogues are given.     

The Biomarkers in the Mesoproterozoic Organic-rich Rocks of North China Craton: Implication for the Precursor and Preservation of Organism in the Prokaryotic Realm

Mesoproterozoic marine organic-rich rocks are widely distributed in the North China Craton,include the Gaoyuzhuang(GYZ),the Hongshuizhuang(HSZ),and the Xiamaling(XML)formations.According to the T;value and isomerisation ratio of C;homohopanes,the XML,HSZ,and GYZ samples were in low mature,mature and high mature stage,respectively.Biomarker distribution in extractable organic matter(EOM)of three Mesoproterozoic organic-rock samples in different maturity were analysed to reveal the organic precursor and preservation pathway of in the Mesoproterozoic Combined with gold-tube pyrolysates of three Mesoproterozoic samples,it could further illuminate the chemical composition of Mesoproterozoic kerogen,given excluding.The results indicated that the three formations were all deposited under reducing condition and their organic precursors mainly were some aquatic organisms.High content of rearranged hopanes was detected in EOM of XML and HSZ samples,whereas they were relatively low in the high mature GYZ sample.Contrast to that in EOM,the relative concentration of rearranged hopanes sharply decreased in the gold-tube pyrolysates of the XML kerogen,then slightly increased but was still significantly lower than the EOM of XML sample,which indicated that catalysis of clay minerals in the early diagenesis only changed the chemical composition of the unstable functional groups of the kerogen during the preservation.Due to the thriving heterotrophic microbes and low sink rate of particulate organic matter during the Mesoproterozoic,primary producers suffered extensive degradation during sinking process,only some resistant biopolymers lacking of lipid compounds survived from heterotrophic degradation,while heterotrophic microbes contained more proportion of organic precursors.Abundant pristane(Pr)and phytane(Ph)were only released in high mature stage because of the protection of the macromolecular structure of resistant biopolymers which prevented biomarkers from being altered by the thermal stress.The absence of 13α(n-alkyl)-tricyclic terpanes in the high matured hydrocarbon products also indicated the different precursors between different parts of Mesoproterozoic kerogen.The evolution of the biomarker composition and content of Mesoproterozoic kerogen showed some special characteristics differing from those of Phanerozoic kerogen.The total concentrations of hopanes displayed with an order of low mature stage>high mature stage>mature stage.Relative content of rearranged hopanes in the hydrocarbon generated in high mature stage was significantly lower than that in the low maturity stage.The ratios of Pr/n-C₁₇ and Ph/n-C₁₈ increased with thermal maturity,and the ratio of nC_21-/nC₂₂₊ decreased in the high maturity stage,thus displaying another order of mature stage>high maturity stage>low maturity stage.The unique preservation pathway of Mesoproterozoic organisms was attributed to the special evolution characteristics of biomarker distributions,which should be considered in the Mesoproterozoic marine environment and biological studies.