桦甸油页岩热解过程中热沥青的组成变化规律.PDF

第44卷 第11期 燃摇 料摇 化摇 学摇 学摇 报 Vol.44 No.11 2016年11月 Journal of Fuel Chemistry and Technology Nov. 2016 文章编号:0253鄄2409(2016)11鄄1310鄄08 桦甸油页岩热解过程中热沥青的组成变化规律 * 畅志兵,初摇 茉 ,张摇 超,白书霞,林摇 浩 (中国矿业大学(北京) 化学与环境工程学院,北京摇 100083) 摘摇 要:将桦甸油页岩分别在300、350、400、450、500 和550 益热解得到半焦,对半焦进行逐级抽提和酸洗,得到自由沥青、碳 酸盐束缚沥青和硅酸盐束缚沥青,采用柱层析、FT鄄IR和GC鄄MS表征不同沥青的化学组成和结构特征,探讨沥青的化学组成 变化及与矿物质的相互作用。 结果表明,沥青总产率先增大后减小并在400 益取得最大值4.63%,400-450 益大量沥青分解 生成页岩油,使沥青产率降至0.98%。 350-450益自由沥青主要发生羧酸脱羧、酯基分解和长链烷烃裂解反应,使羧酸和酯类 化合物含量降低、烷烃碳链长度缩短。 干酪根分解生成的羧酸与碳酸盐反应生成羧酸盐,使400 益碳酸盐束缚沥青中羧酸含 量达78.82%;含氧化合物可与黏土矿物结合,且烷烃可进入蒙脱石层间,使400 益硅酸盐束缚沥青中含氧化合物和烷烃各占 80.79%和19.21%。 关键词:油页岩;热解;热沥青;化学组成 中图分类号:TQ534摇 摇 摇 摇 文献标识码:A Variation of chemical composition of thermal bitumen during Huadian oil shale pyrolysis * CHANG Zhi鄄bing,CHU Mo ,ZHANG Chao,BAI Shu鄄xia,LIN Hao (School of Chemical EnvironmentalEngineering,China University of Mining and Technology (Beijing),Beijing摇 100083,China) Abstract:The variation of chemical composition of thermal bitumen during Huadian oil shale pyrolysis was studied. Spent shale samples obtained by retorting oil shale at 300-550 益 were subjected to sequential Soxhlet extraction鄄acid pickling鄄Soxhlet extraction procedures to obtain free bitumen (FB), bitumen bound with carbonates (BB鄄1) andbitumenboundwith silicates (BB鄄2). Thebitumen sampleswerecharacterizedbyliquid chromatography fractionation,FT鄄IR and GC鄄MS. The results show that the total bitumen yield first increases and thendecreaseswithincreasingtemperaturefrom300to550益,andreachedthemaximumvalueof4.63% at 400 益. Especially,the intense vaporization and