油页岩热解中间产物的反应特性

doi:10.12034/j.issn.1009-606X.217150

过程工程学报 ›› 2017, Vol. 17 ›› Issue (6): 1316-1321.DOI: 10.12034/j.issn.1009-606X.217150

油页岩热解中间产物的反应特性

李梦雅^1,2，战金辉^1*，田勇^1,2，赖登国^1,2，刘晓星¹，许光文¹

1. 中国科学院过程工程研究所多相复杂系统国家重点实验室，北京 100190；2. 中国科学院大学化学与化工学院，北京 100049

收稿日期:2017-02-28 修回日期:2017-04-13 出版日期:2017-12-20 发布日期:2017-12-05
通讯作者: 李梦雅 myli@ipe.ac.cn

Reaction Characteristics of Intermediate Product during Oil Shale Pyrolysis

Mengya LI^1,2, Jinhui ZHAN^1*, Yong TIAN^1,2, Dengguo LAI^1,2, Xiaoxing LIU¹, Guangwen XU¹

1. State Key Laboratory of Multi-phase Complex System, Institute of Process Engineering, CAS, Beijing 100190, China; 2. School of Chemistry and Chemical Engineering, University of Chinese Academy of Sciences, Beijing 100049, China

Received:2017-02-28 Revised:2017-04-13 Online:2017-12-20 Published:2017-12-05

摘要/Abstract

摘要： 对油页岩在不同终温热解所得半焦进行溶剂萃取，得到了热解中间产物(热解沥青)和终产物. 采用气相色谱?质谱联用仪分析了热解沥青和页岩油的组成，采用热裂解?气相色谱?质谱联用仪检测了热解沥青的裂解产物，并与热解页岩油进行对比，研究了油页岩热解沥青的反应特性. 结果表明，油页岩热解沥青在最快产油阶段生成最多且稳定存在，375℃时收率最大；375~400℃时热解产油速率最大，热解沥青收率下降，表明热解沥青在高温下不稳定，有机质生成中间产物后便转化成终产物. 随热解温度升高，热解沥青中轻质组分含量增加. 杂原子化合物最先从有机质上断裂进入中间产物，而热解油中烯烃化合物大部分来自有机质直接裂解，来自热解沥青裂解的较少. 热解温度升高，热解沥青的裂解产物中烯烃含量增加，且热解沥青中芳香烃的长侧链易通过裂解变短.

关键词: 油页岩, 热解中间产物, 反应特性, Py-GC-MS

Abstract: The pyrolysis experiments of oil shale were performed under different ending temperatures, and the pyrolysis intermediate pyrolysis bitumen were obtained by the solution extraction of semicoke. The component analysis of shale oil and pyrolysis intermediate was implemented by gas chromatography?mass spectrometry characterization method. Furthermore, pyrolysis?gas chromatography?mass spectrometry method was used to analyze the distribution of intermediate decomposition products with comparison of pyrolysis of shale oil. The results showed that the intermediate can be produced and stably exist at a limited temperature range of 350~400℃, yield of intermediate reaches the highest value at the temperature of 375℃. The stage of the highest rate for oil-producing occurred at temperature range of 375~400℃, while yield of pyrolysis intermediate started to decrease. Actually pyrolysis intermediate was thermally unstable during the high temperature. The kerogen cracked to form bitumen intermediate and then transformed to final pyrolysis products immediately. The relative content of light components in intermediate increased with rising temperature. Heteroatom-containing compounds can be first released from kerogen and convert into intermediate products. The generation of alkenes in shale oil may be derived from the decomposition of kerogen without experiencing intermediate stage. The long side chains of aromatic hydrocarbons in intermediate can become short by decomposition.

Key words: oil shale, pyrolysis intermediate, reaction characteristic, Py-GC-MS

李梦雅战金辉田勇赖登国刘晓星许光文. 油页岩热解中间产物的反应特性[J]. 过程工程学报, 2017, 17(6): 1316-1321.

Mengya LI Jinhui ZHAN Yong TIAN Dengguo LAI Xiaoxing LIU Guangwen XU. Reaction Characteristics of Intermediate Product during Oil Shale Pyrolysis[J]. Chin. J. Process Eng., 2017, 17(6): 1316-1321.

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油页岩热解中间产物的反应特性

Reaction Characteristics of Intermediate Product during Oil Shale Pyrolysis

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