STUDY OF PYROLYSIS PRODUCTS CHARACTERISTICS OF OIL SHALE KEROGEN

Abstract

Abstract: Py-GC-MS, EPR and FITR techniques were used to analyze the structural characteristics of kerogen and its pyrolysis products in Estonia oil shale. The relationship between the intermediate hot asphalt and the end products were studied at different temperatures. The results show that the pyrolysis of oil shale follows the pyrolysis path of kerogen into intermediate hot bitumen, and then bitumen into shale oil, retort gas and semi-coke. The generation trend of intermediate hot asphalt reflects the change of the growth rate of the final product. H₂, CH₄ and C₂-C₅ are mainly from the aromatization of aliphatic hydrocarbons in hot asphalt, the breaking of alkyl side chains of aromatic compounds and the condensation of oxygen-containing compounds, etc. The alkanes and olefin compounds produced by kerogen pyrolysis are the main components of oil and gas production. The free radical spin concentration of kerogen and shale oil is lower than that of hot asphalt and semi-coke. The g value of semi-coke is the biggest，that of kerogen takes the second place，and the g value of hot asphalt and shale oil is smallest.

Key words: oil shale, pyrolysis, Intermediate, thermal bitumen, kerogen

References

[1] 钱家麟, 尹亮. 油页岩: 石油的补充能源[M]. 中国石化出版社, 2011.
[2] 孙连克, 李森林, 李朋泽. 国内油页岩加工工艺及展望[J]. 燃料与化工, 2013, 44(5):35-38.
[3] 刘招君, 柳蓉. 中国油页岩特征及开发利用前景分析[J]. 地学前缘, 2005, 12(3):315-323.
[4] R.H. MCKEE, LYDER E.E. The Thermal Decomposition of Shales. I—Heat Effects[J]. Ind. Eng. Chem, 1921, 13(7):613-618.
[5] 杨庆春, 张俊, 杨思宇, 等. 油页岩综合利用过程建模与技术经济分析[J]. 化工学报, 2014, 65(7):2793-2801.
[6] V. KATTAI, LOKK U. Historical review of the kukersite oil shale exploration in Estonia[J]. Oil Shale, 1998, 15(2):102-110.
[7] 李宇航, 张宏, 张军华, 等. 油页岩勘探开发现状及进展[J]. CT理论与应用研究, 2014, 23(6):1051-1063.
[8] C.S. Wen, Kobylinski T.P. Low-temperature oil shale conversion[J]. Fuel, 1983, 62(11):1269-1273.
[9] P.R. Solomon, Carangelo R.M., Horn E. The effects of pyrolysis conditions on Israeli oil shale properties[J]. Fuel, 1986, 65(5):650-662.
[10] N.V. Dung. Factors affecting product yields and oil quality during retorting of Stuart oil shale with recycled shale: a screening study[J]. Fuel, 1995, 74(4):623-627.
[11] N. Olukcu, Yanik J., Saglam M., et al. Liquefaction of beypazari oil shale by pyrolysis[J]. Journal of Analytical & Applied Pyrolysis, 2002, 64(1):29-41.
[12] X. Tang, Li S., Yue C., et al. Lumping kinetics of hydrodesulfurization and hydrodenitrogenation of the middle distillate from chinese shale oil[J]. Oil Shale, 2013, 30(4):517-535.
[13] C. Yue, Liu Y., Ma Y., et al. Influence of retorting conditions on the pyrolysis of yaojie oil shale[J]. Oil Shale, 2014, 31(1):66-78.
[14] S. Wang, Liu J., Jiang X., et al. Effect of heating rate on products yield and characteristics of non-condensable gases and shale oil obtained by retorting Dachengzi oil shale[J]. Oil Shale, 2013, 30(1):27-47.
[15] 徐军, 刘瑞斌, 杨金辉, 等. Agilent 6890N型气相色谱仪的日常维护[J]. 实验室科学, 2009, 2009(2): 155-158.
[16] 王擎, 崔达, 迟铭书, 等. 利用GC-MS与NMR技术研究干馏终温对桦甸页岩油组成性质的影响[J]. 化工学报, 2015, 66(7):2670-2677.
[17] 王擎, 李涛. 压力条件对龙口油页岩热解特性的影响[J]. 化工进展, 2017, 36(010):3704-3710.
[18] D. Lai, Chen Z., Lin L., et al. Secondary Cracking and Upgrading of Shale Oil from Pyrolyzing Oil Shale over Shale Ash[J]. Energy & Fuels, 2015, 29(4):2219-2226.