EAP - Oil Shale publications

PUBLISHED
SINCE 1984

Oil Shale

ISSN 1736-7492 (Electronic)
ISSN 0208-189X (Print)

Impact Factor (2022): 1.9

CATALYTIC EFFECTS OF FE- AND CA-BASED ADDITIVES ON GAS EVOLUTION DURING PYROLYSIS OF DACHENGZI OIL SHALE OF CHINA; pp. 39–55

PDF | https//doi.org/10.3176/oil.2018.1.03

Authors

SHA WANG, LIZHI SONG, Xiumin Jiang

Abstract

The pyrolysis of Dachengzi oil shale (OS), Huadian City, China, was carried out in a stainless-steel cylindrical retort at 520 °C both in the absence and presence of catalyst under argon atmosphere to evaluate the catalytic effects of Fe₂O₃ and CaCO₃ additives on the products yield and characteristics of non-condensable gases. The results showed that the catalyst significantly affected the reactivity of OS kerogen pyrolysis. The shale oil yield increased after adding the catalyst, especially Fe₂O₃, but the shale char yield decreased in the presence of the catalyst. The non-condensable gases yield rose in the CaCO₃-catalysed pyrolysis and declined upon the Fe₂O₃-catalysed process, indicating that CaCO₃ had a more pronounced catalytic effect on the secondary reactions of oil vapors. In addition, the gaseous products obtained both with and without the catalyst had a higher volume content of CO₂, CH₄ and H₂, and a lower volume content of CO and C₂–C₄ hydrocarbons. The peak concentrations of CO₂ and H₂ increased in the presence of the catalyst, especially Fe₂O₃, while that of CO enhanced with addition of CaCO₃ as a catalyst. H₂ was generated at higher temperature compared to CO₂ and CO. Furthermore, Fe₂O₃and CaCO₃ exhibited different effects on the evolution of C₁–C₄ hydrocarbons. COS and H₂S evolved almost simultaneously, the amount of H₂S released being higher than that of COS. The peak concentrations of the said gases decreased with adding the catalyst, especially Fe₂O₃. The non-condensable gases produced both before and after catalysis mainly consisted of CO₂ and CH₄, and some minor gases , in terms of mass distribution. The mass contents of ethane, butane, CO₂ and H₂ increased after the use of the catalyst, while those of butane, H₂S and COS decreased. Moreover, adding Fe₂O₃ and CaCO₃ resulted in the decline in the ethene/ethane and propene/propane ratios, respectively, suggesting that different catalysts possibly led to different changes in the physical structure of oil shale and then caused the secondary reactions of pyrolysis products to proceed to different extents. CaCO₃ was more efficient than Fe₂O₃ in producing non-condensable gases of high heating value.

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