U元素在黑色页岩中的富集机理及其对有机质生油气性能的影响

doi:10.13745/j.esf.sf.2024.2.22

摘要/Abstract

摘要：

国内外沉积盆地黑色页岩的形成常伴随着不同程度的U元素富集,厘清黑色页岩中U的富集机理及其对有机矿产形成的影响至关重要。为此本文系统梳理了U元素在有机质、微生物、黏土矿物、含铁矿物、含硫矿物和含磷矿物中的富集过程,并重点阐述了黑色页岩中U元素的赋存机理,以及U元素对有机质生油性能、生气性能和干酪根结构的影响。总体而言,黑色页岩富集U的途径是丰富而多样的,页岩中的多种组分均可通过络合、吸附、还原等方式富集环境中的U元素,富集效率会受到pH、干扰离子浓度等多因素的控制。此外,U对页岩有机质生油气性能的影响也较为复杂,可能是模拟条件和样品存在差异,模拟实验展现出的结果不尽相同,目前仍存在较大争议。尽管诸多学者已开展了大量的研究工作,但国内外关于U元素对有机质影响的研究工作大多数局限于定性分析,目前也存在一些问题亟待解决,主要包括以下几个方面: U元素在黑色页岩中富集的微观机理,难以建立U在黑色页岩中的富集模式;有效表征石油受辐射剂量的指标,难以分析原油的储层滞留时间;人工辐射和自然辐射对有机质生油气影响的异同性,难以揭示有机质在辐射作用下演化的主控因素。未来,应采用先进手段分析辐射影响的微观机理,开展分子组成和结构分析,识别石油中有效的辐解指标,扩展辐射影响在地质领域中的应用。本文对于扩展油气形成机理、探索新型油气资源、丰富黑色页岩中U的地质认识有着较高的借鉴意义。

关键词: U元素, 黑色页岩, 富集机理, 有机质, 生油气性能

Abstract:

The formation of black shale in sedimentary basins, both domestically and internationally, is often associated with varying degrees of uranium (U) enrichment. Understanding the enrichment mechanisms of U in black shale and its impact on the formation of organic minerals is critical. This study systematically reviews the processes of U enrichment in organic matter, microorganisms, clay minerals, iron-bearing minerals, sulfur-bearing minerals, and phosphorus-bearing minerals. It focuses on the mechanisms of U occurrence in black shale and the effects of U on the oil-generation properties, gas-generation properties, and kerogen structure of organic matter. Uranium enrichment in black shale occurs through diverse pathways, with various shale components enriching U in the environment via mechanisms such as complexation, adsorption, and reduction. The efficiency of U enrichment is influenced by multiple factors, including pH and the concentration of interfering ions. Additionally, the impact of U on the oil and gas production performance of shale organic matter is complex and remains controversial, as simulation experiments have yielded inconsistent results due to differences in experimental conditions and sample characteristics. Despite significant research efforts, many studies on the influence of U on organic matter remain limited to qualitative analysis, leaving several critical issues unresolved. These include: (1) the lack of a clear microscopic mechanism for U enrichment in black shale, hindering the development of a comprehensive U enrichment model; (2) challenges in analyzing the reservoir residence time of crude oil due to the difficulty of effectively characterizing the radiation dose of oil; and (3) uncertainties regarding the similarities and differences between the effects of artificial and natural radiation on the oil and gas production performance of organic matter, making it difficult to identify the primary factors controlling the evolution of organic matter under radiation. Future research should employ advanced analytical techniques to investigate the microscopic mechanisms of radiation effects, conduct molecular composition and structural analysis, identify effective radiation indices in oil, and expand the application of radiation studies in geology. This work has significant implications for advancing the understanding of oil and gas formation processes, exploring new oil and gas resources, and enriching geological knowledge about U in black shale.

Key words: U element, uranium, black shale, enrichment mechanism, organic matter, oil-gas performance

中图分类号:

P595

朱紫光, 朱光有, 李茜. U元素在黑色页岩中的富集机理及其对有机质生油气性能的影响[J]. 地学前缘, 2025, 32(2): 290-310.

ZHU Ziguang, ZHU Guangyou, LI Xi. The enrichment mechanism of U element in black shale and its significant influence on the performance of organic matter oil and gas production[J]. Earth Science Frontiers, 2025, 32(2): 290-310.

图/表 8

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富集类型	富集方式	富集机理	价态	实例	数据来源
有机质	络合	有机化合物(富里酸和腐殖酸)和U络合形成稳定的化合物	U(Ⅳ) U(Ⅵ)	有机化合物的类型环境的pH值	文献[12,43-44]
	物理吸附	有机质本身作为一种良好的吸附剂将U吸附在其表面	U(Ⅳ) U(Ⅵ)	环境的pH值	文献[46-47]
	还原	有机质热演化过程中分解的H₂S,CH₄,H₂和NH₃等强还原物质	U(Ⅵ)	温度	文献[16]
微生物	生物还原作用	微生物通过细胞色素、菌毛、电子穿梭体等介质向U传输电子	U(Ⅵ)	乙醇或乙酸盐浓度环境金属离子浓度	文献[49-50,52,54]
	生物吸附作用	U被动且快速地吸附在微生物的表面	U(Ⅳ) U(Ⅵ)	环境pH和离子强度,环境金属离子浓度,环境U浓度	文献[52,66⇓-68]
	生物矿化作用	U在微生物表面沉淀形成结晶或结晶结构	U(Ⅵ)	环境的pH值	文献[72,74-75,77]
	生物积聚作用	微生物主动摄取与微生物必需元素相近的金属元素	U(Ⅳ) U(Ⅵ)	环境pH值碳酸盐碱度	文献[80]
黏土矿物	吸附	黏土矿物的结构表面和颗粒边缘产生电荷对U产生吸附作用	U(Ⅳ) U(Ⅵ)	硫酸盐、碳酸盐、磷酸盐,黏土矿物的类型,环境金属离子浓度,腐殖酸;环境pH	文献[14,81,84-85]
含铁矿物	吸附	含铁矿物本身作为一种良好的吸附剂将U吸附在其表面	U(Ⅳ) U(Ⅵ)	环境pH,碳酸盐浓度	文献[88-89]
含铁矿物	还原	含铁矿物对U的还原主要通过Fe(Ⅱ)来完成	U(Ⅵ)	矿物的表面催化作用, 环境pH,可溶性的Fe(Ⅱ)	文献[15,93]
含硫矿物	吸附	含硫矿物表面不均匀吸附U	U(Ⅵ)	环境pH、溶解性有机质	文献[106]
含硫矿物	还原	含硫基团对U(Ⅵ)的还原	U(Ⅵ)	环境pH	文献[109]
含磷矿物	络合	磷酸盐和U形成稳定的络合物	U(Ⅵ)	环境pH,碳酸盐含量	文献[113,115]

富集类型	富集方式	富集机理	价态	实例	数据来源
有机质	络合	有机化合物(富里酸和腐殖酸)和U络合形成稳定的化合物	U(Ⅳ) U(Ⅵ)	有机化合物的类型环境的pH值	文献[12,43-44]
	物理吸附	有机质本身作为一种良好的吸附剂将U吸附在其表面	U(Ⅳ) U(Ⅵ)	环境的pH值	文献[46-47]
	还原	有机质热演化过程中分解的H₂S,CH₄,H₂和NH₃等强还原物质	U(Ⅵ)	温度	文献[16]
微生物	生物还原作用	微生物通过细胞色素、菌毛、电子穿梭体等介质向U传输电子	U(Ⅵ)	乙醇或乙酸盐浓度环境金属离子浓度	文献[49-50,52,54]
	生物吸附作用	U被动且快速地吸附在微生物的表面	U(Ⅳ) U(Ⅵ)	环境pH和离子强度,环境金属离子浓度,环境U浓度	文献[52,66⇓-68]
	生物矿化作用	U在微生物表面沉淀形成结晶或结晶结构	U(Ⅵ)	环境的pH值	文献[72,74-75,77]
	生物积聚作用	微生物主动摄取与微生物必需元素相近的金属元素	U(Ⅳ) U(Ⅵ)	环境pH值碳酸盐碱度	文献[80]
黏土矿物	吸附	黏土矿物的结构表面和颗粒边缘产生电荷对U产生吸附作用	U(Ⅳ) U(Ⅵ)	硫酸盐、碳酸盐、磷酸盐,黏土矿物的类型,环境金属离子浓度,腐殖酸;环境pH	文献[14,81,84-85]
含铁矿物	吸附	含铁矿物本身作为一种良好的吸附剂将U吸附在其表面	U(Ⅳ) U(Ⅵ)	环境pH,碳酸盐浓度	文献[88-89]
含铁矿物	还原	含铁矿物对U的还原主要通过Fe(Ⅱ)来完成	U(Ⅵ)	矿物的表面催化作用, 环境pH,可溶性的Fe(Ⅱ)	文献[15,93]
含硫矿物	吸附	含硫矿物表面不均匀吸附U	U(Ⅵ)	环境pH、溶解性有机质	文献[106]
含硫矿物	还原	含硫基团对U(Ⅵ)的还原	U(Ⅵ)	环境pH	文献[109]
含磷矿物	络合	磷酸盐和U形成稳定的络合物	U(Ⅵ)	环境pH,碳酸盐含量	文献[113,115]