油页岩流化床干馏过程的热化学反应机理与成油过程调控机制

The fluidized bed retorting technology of oil shale has many advantages, such as uniform temperature distribution, low coking reaction and high oil yield, showing good application prospects for oil shale. Many investigations have been performed about this kind of retorting technology, mainly focusing on the effects of retorting processes and operating parameters on the oil yield. However, there are little concerns on the thermochemical reaction mechanism and shale oil regulating mechanism of oil shale fluidized bed retorting. Consequently, this project will first experimentally study chemical structure characteristics of oil shale and its fundamental thermochemical conversion characteristics. And the thermochemical reactions of oil shale will be simulated by means of the Reactive Force Field (ReaxFF) molecular dynamics. A lab-scale fluidized bed retorting system of oil shale will be built for exploring the retorting characteristics of oil shale in the fluidized bed. Combined the experimental results with the molecular mechanism of thermochemical conversions of oil shale, the formation history of shale oil in the fluidized bed will revealed. This project will optimize the fluidized bed retorting parameters and moreover add hydrogen rich fuels during the retorting of oil shale, in order to regulate the reaction ways of the precursors of shale oil for higher yield and quality of shale oil with a good combustion activity of oil shale semicoke. This project can provide the basic data and theoretical guidance for developing the fluidized bed retorting technology of oil shale.

油页岩流化床干馏技术具有温度分布均匀、油气二次焦化反应程度低、油产率高等诸多优点，具有良好的发展前景。目前有关油页岩流化床干馏特性的研究已有一定文献报道，但主要关注于技术路线和工艺参数等宏观因素对页岩油产率影响的研究，有关油页岩在流化床内热化学转化机理与干馏反应中间过程调控机制的研究鲜见报道。本项目以油页岩流化床干馏技术为背景，实验研究油页岩化学结构成键特性与热化学转化基础特性，借助ReaxFF反应分子动力学模拟方法揭示油页岩热化学反应分子机理，在自行设计、搭建的流化床干馏实验系统上研究油页岩在流化床内干馏特性，结合油页岩热化学反应分子机理揭示页岩油在流化床内形成机理，采用优化流化床干馏参数和添加富氢燃料共干馏的手段调控页岩油前驱物的热化学反应路径，在保持油页岩半焦燃烧活性的条件下提高页岩油产率和品质，为油页岩流化床干馏技术的研发提供基础数据与理论指导。

实现储量巨大的油页岩资源高效清洁干馏利用对于我国应对原油对外依存度过高的局势意义重大。油页岩流化床干馏技术是近些年发展起来的一项新兴干馏技术，具有温度分布均匀、油气二次焦化反应程度低、油产率高等诸多优点，但有关油页岩在流化床内热化学转化机理以及反应过程调控机制的研究尚属空白。本项目采取实验研究、量子化学计算与分子动力学模拟相结合的方法，对吉林桦甸油页岩化学结构特征、热化学转化分子机理、油页岩流化床干馏特性、页岩油形成机理以及油页岩流化床干馏过程调控措施等进行了系统、深入的研究，取得的研究成果包括：精确表征并构建了油母质大分子结构模型，通过反应分子动力学模拟从分子层面揭示了油母质的热化学反应机理；首次全面研究了干馏温度、载气流量、颗粒粒度和给料速率等参数对油页岩流化床干馏特性的影响，为工业油页岩流化床干馏技术的研发奠定了基础；揭示了页岩油的形成机理以及富氢环境对页岩油各类化学键断裂和有机O、N和S杂原子转化的影响机制，为提高页岩油产率和品质提供了基础数据与理论指导；揭示出页岩油在慢速和快速升温速率下的热解行为，模拟分析了页岩油关键组分的模型化合物和裂解反应机理，探索了油页岩流化床干馏过程的多维度调控策略。基于上述研究成果，提出油页岩双床不等温鼓泡床干馏-半焦循环流化床燃烧一体化技术路线，完成兖矿能源集团股份有限公司《150万吨/年油页岩分质清洁高效利用项目方案》建议书的编制。在本基金的资助下，发表SCI论文15篇，Web of Science核心库SCI他引80次；另有3篇SCI论文处于审稿中；培养博士研究生5名。