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超临界二氧化碳诱导油页岩压力控制热解中挥发性产物的释放机制

Release Mechanism of Volatile Products from Oil Shale Pressure-Controlled Pyrolysis Induced by Supercritical Carbon Dioxide.

作者信息

Zhao Shuai, Su Jianzheng, Wu Junwen, Xiaoshu Lü

机构信息

State Key Laboratory of Shale Oil and Gas Enrichment Mechanisms and Effective Development, Beijing 1100083, China.

State Center Research and Development of Oil Shale Exploitation, Beijing 1100083, China.

出版信息

ACS Omega. 2022 Dec 9;7(50):47330-47340. doi: 10.1021/acsomega.2c06693. eCollection 2022 Dec 20.

Abstract

The compactness of the oil shale reservoir and the complexity of the pore structure lead to the secondary reaction of kerogen in the process of hydrocarbon expulsion, which reduces the effective recovery of shale oil. In this paper, supercritical carbon dioxide was used as a heat carrier and a displacement medium. In a self-designed fluidized bed experimental system for pressure-controlled pyrolysis of oil shale, the experiments of oil shale pyrolysis under standard atmospheric pressure and 7.8-8.0 MPa pressure in nitrogen and carbon dioxide atmospheres were completed. The extraction efficiency of supercritical carbon dioxide at low temperature is obvious, but with the increase of temperature, the effect of extraction on pyrolysis is lower than that of temperature. Under a nitrogen atmosphere, the secondary reaction of shale oil is mainly secondary pyrolysis and aromatization. However, in a supercritical carbon dioxide atmosphere, the main reactions are secondary addition and aromatization. In addition, compared with that in the standard atmospheric pressure, it was found that the olefin synthesis reaction was obviously inhibited under a high-pressure nitrogen or supercritical carbon dioxide atmosphere.

摘要

油页岩储层的致密性和孔隙结构的复杂性导致干酪根在排烃过程中发生二次反应,从而降低了页岩油的有效采收率。本文以超临界二氧化碳作为热载体和驱替介质,在自行设计的油页岩压力控制热解流化床实验系统中,完成了油页岩在氮气和二氧化碳气氛下标准大气压以及7.8 - 8.0 MPa压力下的热解实验。超临界二氧化碳在低温下的萃取效率明显,但随着温度升高,萃取对热解的影响低于温度的影响。在氮气气氛下,页岩油的二次反应主要是二次热解和芳构化。然而,在超临界二氧化碳气氛下,主要反应是二次加成和芳构化。此外,与标准大气压下相比,发现在高压氮气或超临界二氧化碳气氛下烯烃合成反应明显受到抑制。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/560f/9774379/fb49e9c3fe1f/ao2c06693_0002.jpg

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