油页岩共价键分布及其加氢热解特征  

Distribution and hydropyrolysis of the covalent bonds in oil shales

作　　者：周斌 赵晓胜 李哲 周友 王艺霏 赵璐璐 ZHOU Bin;ZHAO Xiaosheng;LI Zhe;ZHOU You;WANG Yifei;ZHAO Lulu(New Energy Technology Development Center,National Institute of Clean and-Low-Carbon Energy,Beijing 102211,China;College of Chemistry and Chemical Engineering,Cangzhou Normal University,Cangzhou 061001,Hebei,China)

机构地区：[1]北京低碳清洁能源研究院新能源技术研究中心,北京102211 [2]沧州师范学院化学与化工学院,河北沧州061001

出　　处：《洁净煤技术》2023年第5期39-45,共7页Clean Coal Technology

基　　金：北京低碳清洁能源研究院研发资助项目(KJ9300000286)。

摘　　要：面对我国贫油的现状,开发利用油页岩引起了广泛关注。然而,油页岩有机结构的复杂性制约了其清洁高效转化技术的发展。为从微观层面认识油页岩结构与其反应性的关系(简称构效关系),研究了8种油页岩的共价键特征,并利用人工神经网络(Artificial Neural Network,ANN)以R2>0.99的高精度量化了油页岩共价键分布、反应温度、反应时间与自由基加氢量的关系。敏感度分析结果表明油页岩中的C_(al)—C_(al)、C_(al)—C_(ar)、C_(ar)—C_(ar)、C_(al)—O、C_(ar)—O和C_(al)=O会促进自由基的产生及加氢;C_(al)—H和C_(ar)—H发生断键产生的C_(al)·和C_(ar)·会发生缩聚反应,而产生的H·会给其他自由基加氢,间接抑制了溶剂加氢行为;O—H在反应中断键的可能性较低。该研究对油页岩、煤、生物质的温和转化技术具有借鉴意义。The utilization of oil shales earns popularity due to the shortage of petroleum of China.However,the clean and efficient conversion of oil shales is limited due to the complexity of the organic matters in oil shales.To understand the structure-reactivity relationship of oil shales in a micro-level,this work studied the distribution characteristics of the covalent bonds of 8 oil shales,and used Artificial Neural Network(ANN)to precisely quantify the relationship between bond distributions,reaction temperature,reaction time and the abundance of free radicals that were generated in pyrolysis and then captured by H from hydrogen-donor solvent.From the sensitivity analysis,the C_(al)—C_(al),C_(al)—C_(ar),C_(ar)—C_(ar),C_(al)—O,C_(ar)—O and C_(al)=O in oil shales could facilitate the generation and hydrogenation of free radicals in hydropyrolysis.While the C_(al)·and C_(ar)·generated from the breakage of C_(al)—H and C_(ar)—H in oil shales tend to take part in the coupling and condensation reactions.Meanwhile,H·from the breakage of C_(al)—H and C_(ar)—H can capture free radicals,decreasing the hydrogenation effect of hydrogen-donor solvent.And the breakage of O—H of oil shales in the reaction is of low-possibility.The above results to some degrees highlight the mild thermal-conversion technologies of oil shales,coals and biomass.

关 键 词：油页岩 共价键 供氢溶剂加氢热解 人工神经网络 敏感度分析 

分 类 号：TQ517[化学工程]