石油学报 ›› 2020, Vol. 41 ›› Issue (7): 796-808.DOI: 10.7623/syxb202007002

• 地质勘探 • 上一篇    下一篇

煤中金刚烷的分布与演化

马安来1,2, 金之钧1, 晏继发3, 米敬奎4, 李杰豪5   

  1. 1. 中国石油化工股份有限公司石油勘探开发研究院 北京 100083;
    2. 有机地球化学国家重点实验室 广东广州 510640;
    3. 中国矿业大学(北京)地球科学与测绘工程学院 北京 100083;
    4. 中国石油勘探开发研究院 北京 100083;
    5. 中国地质大学(北京)能源学院 北京 100083
  • 收稿日期:2019-08-20 修回日期:2020-01-16 出版日期:2020-07-25 发布日期:2020-08-08
  • 通讯作者: 马安来,男,1969年12月生,1991年获淮南矿业学院学士学位,2003年获中国石油勘探开发研究院博士学位,现为中国石油化工股份有限公司石油勘探开发研究院副教授,主要从事油气地球化学与成藏机理研究。
  • 作者简介:马安来,男,1969年12月生,1991年获淮南矿业学院学士学位,2003年获中国石油勘探开发研究院博士学位,现为中国石油化工股份有限公司石油勘探开发研究院副教授,主要从事油气地球化学与成藏机理研究。Email:maal.syky@sinopec.com
  • 基金资助:

    国家自然科学基金项目(No.41772153,No.U19B6003-02)、有机地球化学国家重点实验室开放基金项目(SKLOG-201702)和中国石油化工股份有限公司科技部项目(P17049-1,P19024)资助。

Distribution and evolution of diamondoids in coals

Ma Anlai1,2, Jin Zhijun1, Yan Jifa3, Mi Jingkui4, Li Jiehao5   

  1. 1. Sinopec Petroleum Exploration & Production Research Institute, Beijing 100083, China;
    2. State Key Laboratory of Organic Geochemistry, Guangdong Guangzhou 510640, China;
    3. School of Geosciences and Surveying Engineering, China University of Mining and Technology, Beijing 100083, China;
    4. PetroChina Research Institute of Petroleum Exploration and Development, Beijing 100083, China;
    5. School of Energy Resources, China University of Geosciences, Beijing 100083, China
  • Received:2019-08-20 Revised:2020-01-16 Online:2020-07-25 Published:2020-08-08

摘要:

金刚烷的浓度和指数是研究深层油藏裂解程度和成熟度的重要参数,由于金刚烷的形成机理不明,制约了金刚烷化合物在深层油气地球化学中的应用。通过对华北地区镜质体反射率(Ro)在0.55%~5.32%的二叠系煤样开展金刚烷色谱-质谱定量分析,发现低成熟煤样中存在单金刚烷系列化合物,而煤样中双金刚烷、三金刚烷和四金刚烷系列化合物的检出所对应的Ro分别为0.81%、1.82%和2.59%。这表明不同笼数金刚烷的生成具有阶段性,笼数越高,其所对应的烃源岩成熟度越高。定量分析结果表明,煤样在Ro为0.55%~3.01%时为金刚烷生成阶段,煤样在Ro>3.01%时对应金刚烷裂解阶段,其中,当Ro>2.71%,单金刚烷系列和双金刚烷系列的组成发生变化。金刚烷参数,如二甲基单金刚烷指数1(DMAI1)、二甲基单金刚烷指数2(DMAI2)、三甲基单金刚烷指数1(TMAI1)、三甲基单金刚烷指数2(TMAI2)以及乙基单金刚烷(EA)参数[1-EA/(1-EA+2-EA)],与Ro在0.55%~3.01%阶段具有较好的正相关。金刚烷产率的比值,如二甲基单金刚烷系列与二甲基双金刚烷系列比值、甲基单金刚烷系列与甲基双金刚烷系列比值、单金刚烷系列与双金刚烷系列比值以及单金刚烷与双金刚烷比值,与Ro在0.81%~4.28%阶段具有明显的负相关关系,表明这些参数可以用作评价成熟度的良好指标。

关键词: 金刚烷, 单金刚烷, 双金刚烷, 三金刚烷, 四金刚烷, 镜质体反射率, 成熟度演化, 二叠系,

Abstract:

The concentration and index of diamondoids are the key parameters for evaluating the cracking degree and maturity of deep reservoirs. The formation mechanism of diamondoids is unknown, which restricts the application of diamondoid compounds in petroleum geochemical exploration of deep strata. Through the quantitative analysis of diamondoids by gas chromatography-mass spectrometry on the Permian coal samples with the vitrinite reflectance (Ro) of 0.55%-5.32% in North China, it was found that the adamantane series existed in the low-mature coal samples. The Ro corresponding to the diamantane, triamantane and tetramantane series in the coal samples were 0.81%, 1.82% and 2.59%, respectively. This indicates the staged generation of diamondoids with different cage units. The higher the cage unit is, the higher the corresponding maturity of the source rock will be. The quantitative analysis results show that the Ro of coal sample in the range of 0.55%-3.01% indicate the generation stage of diamondoids, while the Ro greater than 3.01% indicates the cracking stage of diamondoids. When Ro>2.71%, the composition of the adamantane and diamantane series changed. Diamondoid parameters, such as the dimethyladamantane index 1 (DMAI1), dimethyladamantane index 2 (DMAI2), trimethyladamantane index 1 (TMAI1), trimethyladamantane index 2 (TMAI2) and ethyladamantane (EA) parameter[1-EA/(1-EA+2-EA)], have a good positive correlation with Ro in the range of 0.55%-3.01%. The ratios of diamondoid yield, such as the ratio of dimethyl adamantanes series to dimethyl diamantanes series, the ratio of methyl adamantanes series to methyl diamantanes series, the ratio of adamantanes series to diamantanes series and the ratio of adamantine to diamantane, has a significant negative correlation with Ro in the range of 0.81%-4.28%, indicating that these parameters can be used as good indicators for evaluating the maturity of source rock.

Key words: diamondoid, adamantanes, diamantanes, triamantanes, tetramantanes, vitrinite reflectance, maturity evolution, Permian, coal

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