水介质条件下油页岩热解机理研究-燃料化学学报.PDF

第39卷 第12期 燃摇 料摇 化摇 学摇 学摇 报 Vol.39 No.12 2011年12月 Journal of Fuel Chemistry and Technology Dec. 2011 文章编号:0253鄄2409(2011)12鄄0881鄄06 水介质条件下油页岩热解机理研究 1 1 2 3 马摇 跃 ,李术元 ,王摇 娟 ,方朝合 (1.中国石油大学(北京) 重质油国家重点实验室,北京摇 102249; 2.北京国电富通科技发展有限责任公司,北京摇 100070;3.中国石油勘探开发研究院廊坊分院,河北 廊坊摇 065007) 摘摇 要:利用高压釜反应装置,对柳树河油页岩进行了饱和水和不饱和水介质条件下的热压模拟实验,研究了两种条件下油 页岩热解产物(气体、油和热沥青)的生成机理。 实验结果表明,在油页岩的热解过程中,同时经历自由基反应和碳正离子反 应。 水在高温的物化性质较在常温常压时发生了巨大的变化,具有酸催化剂和碱催化剂的作用,促使按碳正离子机理进行反 应;另一方面,由于油页岩结构中键的类型很多,一部分也按自由基反应进行降解。 关键词:油页岩;水介质;机理; 自由基反应;碳正离子反应 中图分类号:O621.1摇 摇 文献标识码:A Mechanism of oil shale pyrolysis under high pressurewater 1 1 2 3 MA Yue ,LI Shu鄄yuan ,WANG Juan ,FANG Chao鄄he (1.State Key Laboratory of Heavy OilProcessing,China University of Petroleum(Beijing),Beijing摇 102249,China; 2.Guodianfutong Science and Technology Development Co. ,LTD,Beijing摇 100070,China; 3.PetrochinaResearchInstitute of Petroleum Exploration Development鄄Langfang,Langfang摇 065007,China) Abstract:The pyrolysis experiments of oil shale from Liushuhe were performed by using an autoclave with saturated or unsaturated water. The formation mechanism of pyrolysate including retorting gas,oil and bitumen was discussed. It is found that the free radical and carbocation reactions occur simultanously during oil shale pyrolysis. Thephysicaland chemicalpropertiesof water athigh pressureandtemperatureare very different from those at normal temperatureandpressure,which canpromotethecarbocationreaction ofoil shaleastheacidand alkali catalyst. At the same time,the freeradicalreaction also occursbecause of the diversity in chemicalbonds of oil shale. Key words:oil shale;aqueousmedium;mec