硅藻及其絮凝体——松辽盆地古龙页岩轻质油的主要贡献者
作者:
基金项目:

本文为国家自然科学基金项目(编号42072138,41572088)、中国石油天然气股份有限公司重大科技专项(编号2021ZZ10)和黑龙江省“百千万”工程科技重大专项(编号2020ZX05A01)联合资助的成果


Diatoms and their aggregates: The main contributor to the light oil of Gulong shale in Songliao basin
Author:
  • 摘要
  • | |
  • 访问统计
  • |
  • 参考文献
  • |
  • 相似文献
  • |
  • 引证文献
  • | |
  • 文章评论
    摘要:

    通过岩芯精细观察描述、薄片鉴定和场发射、能谱、XRD及色质联用等分析,研究了古龙青山口组页岩及其轻质油,发现古龙凹陷青山口组页岩中发育了大量硅藻及硅藻絮凝体,是古龙青山口组轻质页岩油的主要贡献者。能谱分析表明,硅藻及硅藻絮凝体硅氧含量很高,Si/Al比值介于2. 88~15. 20,平均6. 65,远大于伊利石Si/Al比值(1. 82)(实际测定),揭示了有较多的Si是以SiO2的方式存在,是硅藻多胺诱导形成的生物石英,其颗粒极其细小,直径多在数微米,是古龙凹陷青山口组页岩中超细石英(直径<3. 9 μm)的主要来源。古龙青山口组页岩中的沥青和渗出油富N,N含量介于7. 26%~46. 40%,间接地证明了古龙青山口组页岩中有大量硅藻。硅藻含有丰富的多胺和脂肪酸,通过成岩作用多胺形成了古龙页岩轻质油中的汽油,脂肪酸形成了柴油。硅藻多胺通过成岩作用去硝基化形N- 二甲基丙胺,进一步去硝基和脱甲基聚合形成古龙青山口组轻质油中的C12以下的烷烃,其中C8为主峰;古龙页岩轻质油还有另一个主峰(C15),是由硅藻的以C16为主的脂肪酸脱羧基还原形成的。硅藻中C16脂肪酸占总量的55. 4%,其经过脱羧加H可以形成C15烷烃(柴油的主峰),从机理上解释了柴油的主峰是C15的原因。古龙页岩轻质油中的柴油峰与现代硅藻不饱和脂肪酸的C数和质量都具有较好的对应关系,故推测古龙轻质页岩油的柴油是由硅藻脂肪酸形成的。古龙青山口组页岩中的轻质油是一种分馏轻质油,不是热裂解轻质油。

    Abstract:

    The Qingshankou Formation shale and its associated light oil in the Gulong sag were studied through detailed core observation, thin section analysis, field emission scanning electron microscopy (FE- SEM), energy- dispersive X- ray spectroscopy (EDS), X- ray diffraction (XRD), and gas chromatography. The study revealed that the shale contains abundant diatoms and diatom flocs, which played a significant role in the formation of the light oil. EDS analysis indicates that the silica content of diatoms and diatom flocs is exceptionally high, the Si/Al ratio ranges from 2. 88 to 15. 20, with an average of 6. 65, significantly higher than the Si/Al ratio of illite (1. 82, based on measurements of modern clay). This suggests that a substantial portion of the silica exists as biosilica, specifically biological quartz formed by diatoms through polyamine- induced biomineralization. The biosilica particles are extremely small, with diameters of several microns, and represent the primary source of ultrafine quartz particles (diameter<3. 9 μm) in the Qingshankou Formation shale of the Gulong sag. The bitumen and oil in the Qingshankou Formation shale are rich in N, with concentrations ranging from 7. 26% to 46. 40%. This indirectly confirms the presence of abundant diatoms, as diatoms are rich in polyamines. Polyamines and fatty acids in diatoms undergo diagenesis transformations to form hydrocarbons: polyamines contribute to the formation of gasoline, while fatty acids contribute to the formation of diesel oil in the Gulong shale light oil. Specifically, diatomaceous polyamines undergo denitration to form N- dimethylpropylamine, which further undergoes denitration and demethylation polymerization to produce alkanes below C12, with C8 as the main peak. Another prominent peak in the Gulong shale light oil is C15, which is formed by the decarboxylation and reduction of C16- dominated fatty acids derived from diatoms. Diatoms also contain a significant proportion of C16 fatty acids, accounting for 55.4% of the total fatty acids. The C15 alkane (the main peak of diesel oil) can be formed from C16 fatty acid after decarboxylation and hydrogenation. In addition, C16 fatty acids can also be converted into C16 and C17 alkanes (45. 57% of the light oil) through methylation and ethylation, respectively. Octadecenoic acid and eicosenic acid in diatoms account for about 33. 4% of the total fatty acids, closely matching the paraffin ratio (30. 70%) of octadecane, nonadecane, eicosane, and heneicosane in the shale oil of Qingshankou Formation. Both qualitative or quantitative analyses demonstrate a strong correspondence between the diesel peak in Gulong shale light oil and the carbon number and composition of modern diatom unsaturated fatty acids. This provides reliable evidence that the diesel fraction of Gulong light shale oil is formed by diatom fatty acids. Gulong shale light oil in Qingshankou Formation is a kind of fractionated light oil and not pyrolytic light oil.

    参考文献
    相似文献
    引证文献
引用本文

何文渊,白雪峰,张金友,付秀丽,赵莹,钟建华,孙宁亮,圣朋朋.2025.硅藻及其絮凝体——松辽盆地古龙页岩轻质油的主要贡献者[J].地质学报,99(5):1690-1710.
HE Wenyuan, BAI Xuefeng, ZHANG Jinyou, FU Xiuli, ZHAO Ying, ZHONG Jianhua, SUN Ningliang, SHENG Pengpeng.2025. Diatoms and their aggregates: The main contributor to the light oil of Gulong shale in Songliao basin[J]. Acta Geologica Sinica,99(5):1690-1710.

复制
分享
文章指标
  • 点击次数:
  • 下载次数:
  • HTML阅读次数:
  • 引用次数:
历史
  • 收稿日期:2024-02-05
  • 最后修改日期:2024-05-13
  • 录用日期:2024-05-22
  • 在线发布日期: 2025-01-26