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.
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.
[1]钱家麟, 尹亮, 王剑秋,等. 油页岩—石油的补充能源 [M]. 北京:中国石油出版社, 2008: 78-80.<br>[2]XIE FF, W Z, LIN WG,et al. Study on thermal conversion of Huadian oil shale under N<sub>2</sub> and CO<sub>2</sub> atmosphere [J]. Oil Shale, 2010, 27(40): 309-320.<br>[3]杨庆春, 周怀荣, 杨思宇,等. 油页岩开发利用技术及系统集成的研究进展 [J]. 化工学报, 2016, 67(1): 109-118.<br>[4]THAKUR D S, NUTTALL H E J. Kinetics of Pyrolysis of Moroccan Oil Shale by Thermogravimetry [J]. Ind. Eng. Chem. Res., 1987, 26: 1351-1356.<br>[5]LI S Y, YUE C T. Study of different kinetic models for oil shale pyrolysis [J]. Fuel Processing Technology, 2003, 85: 51-61.<br>[6]HUBBARD A B, ROBINSON W E. Thermal Decomposition Study of Colorado Oil Shale [J]. U.S. Bur. Mines, Rept. Inv. 4744, 1950.<br>[7]BURNHAM A K. Chemistry and kinetics of oil shale retorting [J]. Oil Shale A Solution to the Liquid Fuel Dilemma, 2010, 1032:115-134. <br>[8]WEN C S, KOBYLINSKI T P. Low-temperature oil shale conversion [J]. FUEL, 1983, 62: 1269-1273.<br>[9]ZAIDENTSAL A L, SOONEA J H, MUONI R T. Yields and Properties of Thermal Bitumen Obtained from Combustible Shale [J]. Solid Fuel Chemistry, 2008, 42: 74-79.<br>[10]DOAN T V L, BOSTROM N W, BURNHAM A K,et al. Green River Oil Shale Pyrolysis: Semi-Open Conditions [J]. Energy Fuels, 2013, 27: 6447-6459.<br>[11]WANG S, JIANG X M, HAN XX,et al. Effect of retorting temperature on product yield and characteristics of non-condensable gases and shale oil obtained by retorting Huadian oil shales [J]. Fuel Processing Technology, 2014, 121: 9-15.<br>[12]SOLUM M S, MAYNE C L, ORENDT A M,et al. Characterization of Macromolecular Structure Elements from a Green River Oil Shale, I. Extracts [J]. Energy Fuels, 2014, 28: 453-465.<br>[13]CRADDOCK P R, DOAN T V L, BAKE K,et al. Evolution of Kerogen and Bitumen during Thermal Maturation via Semi-Open Pyrolysis Investigated by Infrared Spectroscopy [J]. Energy Fuels, 2015, 29: 2197-2210.<br>[14]TIIKMA L, ZAIDENTSAL A, TENSORER M. FORMATION OF THERMOBITUMEN FROM OIL SHALE BY LOW-TEMPERATURE PYROLYSIS IN AN AUTOCLAVE [J]. Oil Shale, 2007, 24: 535-546.<br>[15]LI Q Y, HAN X X, LIU Q Q,et al. Thermal decomposition of Huadian oil shale. Part 1. Critical organic intermediates [J]. Fuel, 2014, 121: 109-116. <br>[16]杨博宁, 赵德智, 刘美. 裂解色谱在石油和化工领域的应用现状 [J]. 应用化工, 2015, 44(6): 1127-1129.<br>[17]WILLIAMS P F V. Thermogravimetry and decomposition kinetics of British Kimmeridge Clay oil shale [J]. Fuel, 1985, 64(4):540-545.<br>[18]WANG Q, SUN B Z, HU A J,<i>et</i><i> al</i>. Pyrolysis characteristics of Huadian oil shales [J]. Oil Shale, 2007, 24(2):147-157.<br>[19]李术元, 钱家麟, 秦匡宗,等. 沥青作为中间产物的油页岩热解动力学的研究 [J]. 燃料化学学报, 1987, 15(2): 118-123.<br>[20]王擎,黄宗越,迟铭书,等. 油页岩干酪根化学结构特性分析 [J]. 化工学报, 2015, 66(5):1861-1866.<br>[21]CHEN B, HAN X X, LI Q Y,et al. Study of the thermal conversions of organic carbon of Huadian oil shale during pyrolysis [J]. Energy Conversion and Management, 2016, 127: 284-292.<br>