干酪根热解生烃分子模拟研究进展  

Progress of Kerogen Pyrolysis for Hydrocarbon Generation Using Molecular Simulation

作　　者：郭成波 李美俊[1] 刘晓强 韩秋雅 GUO ChengBo;LI MeiJun;LIU XiaoQiang;HAN QiuYa(State Key Laboratory of Petroleum Resources and Prospecting,College of Geosciences,China University of Petroleum(Beijing),Beijing 102249,China;College of Chemistry and Environment,Sichuan University of Science&Engineering,Zigong,Sichuan 643000,China)

机构地区：[1]中国石油大学(北京)地球科学学院,油气资源与探测国家重点实验室,北京102249 [2]四川轻化工大学化学与环境工程学院,四川自贡643000

出　　处：《沉积学报》2024年第5期1494-1511,共18页Acta Sedimentologica Sinica

基　　金：国家自然科学基金项目(42173054)。

摘　　要：【意义】干酪根是世界上最丰富的天然有机质来源,研究干酪根的热解对油页岩的开发利用具有重要的意义。传统的热解生烃模拟实验难以深入揭示干酪根热解机理,而分子模拟方法可从原子分子水平上深入揭示干酪根热解的微观机理,是一种重要的研究手段。【进展】对干酪根热解生烃的分子模拟研究进展进行了述评,并结合实验结果,分别阐述了温度、升温速率、水、压力、页岩矿物组分对于干酪根热解的影响。主要有:(1)构建干酪根分子结构模型最常用的方法是基于实验分析方法中获得的元素、官能团信息和结构参数;(2)温度、升温速率、水、压力、页岩矿物组分对干酪根热解产物分子数和组分均存在不同程度的影响,选择合适的温度和升温速率可以使得页岩油的产率达到最大;(3)H2O分子可促进干酪根和重质页岩油的裂解,提高轻质页岩油和气体的产率;(4)对比分子模拟结果与实验结果发现,分子模拟在定量描述方面具有较大的优势,而在定性描述方面稍显不足;(5)分子模拟通常采用提高模拟温度的方法进而缩短反应时间来弥补地质上的热演化时间,这是目前分子模拟技术的缺陷之一;(6)干酪根的高温模拟会产生大量的C2H4,这与实验事实和地质概况不符,也是当前分子模拟的不足之处。【展望】展望未来,干酪根热解生烃分子模拟研究可在以下方面取得发展:(1)使用机器学习法快速构建相对分子量达上百万,并且同时反映干酪根化学结构和孔隙结构的分子结构模型;(2)建立富含页岩矿物组分、地层水、有机酸以及无机盐等多尺度且复杂的干酪根模型;(3)深入研究升温速率、水的相态、地层水、压力、矿物组分以及不同热演化程度对干酪根热解的影响;4)结合实际地质概况探索低温条件下干酪根的热解生烃机制,进而弥补实验—地质—理论之间的鸿沟,为页[Significance]Kerogen is the most abundant source of natural organic matter in the world.It is important to study the pyrolysis of kerogen for the exploitation and utilization of oil shales.The traditional pyrolysis experiment cannot easily reveal the mechanism of kerogen pyrolysis,but the molecular simulation method can expose the microscopic mechanism of kerogen pyrolysis at the atomic and molecular level,which is an important research method.[Progress]In this study,the research progress of molecular simulation of kerogen pyrolysis was systematically reviewed.Combined with the experimental results,the effects of temperature,heating rate,water,pressure,and shale mineral composition on kerogen pyrolysis were described.The results showed:(1)The most commonly used method for constructing a kerogen molecular structure model is based on the elements,functional groups,and structural parameters obtained from experimental analysis methods.(2)Temperature,heating rate,water,pressure,and shale mineral components all have varying degrees of influence on the molecular number and components of kerogen pyrolysis products.In general,the number of molecules undergoing kerogen pyrolysis increases with the increase in temperature.High temperature is not conducive to the direct pyrolysis process but helps to fully conduct the reaction in the hydropyrolysis process.An increase in heating rate increases the temperature at which kerogen begins to pyrolyze.The number of molecules produced by the pyrolysis of kerogen increases with the increase in heating rate,but a high heating rate reduces the number of molecules produced by pyrolysis.Choosing the appropriate temperature and heating rate can maximize the yield of shale oil.(3)Water molecules can provide more hydrogen radicals to participate in the reaction,thereby promoting the cracking of kerogen and heavy shale oil,hindering the formation of C-C crosslinking structure,and improving the formation of light shale oil and gas yields.(4)Compared with the experimental results,molecular si

关 键 词：干酪根 分子结构模型 热解机理 分子动力学模拟 ReaxFF力场 

分 类 号：P618.13[天文地球—矿床学]