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Prediction of gaseous products from Dachengzi oil shale pyrolysis through combined kinetic and thermodynamic simulations

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Abstract

The characteristics of gas evolution from Dachengzi oil shale pyrolysis under different temperatures were experimentally investigated using a fixed bed reactor and then were evaluated by integrating thermodynamic equilibrium simulation employing HSC Chemistry program and Sandia PSR kinetics simulation in this paper. The experiment results indicate that the non-condensable gases contain much higher CO2, CH4 and H2 and lower CO and C2–C4 hydrocarbons in terms of volume percentages, and mainly consist of CO2 and CH4 as well as some minor gases in terms of mass distribution. CO2, CO and H2 are firstly produced followed by the generation of light hydrocarbons. The HSC calculation results present that some C2 and C2+ hydrocarbons disappear in the predicted gaseous products thermodynamically, and the nitrogen- and sulfur-containing gases mainly are N2 and H2S, respectively. Then, the normalized HSC species are inputted into the Sandia PSR code by three methods, i.e., the CHO input method, the regional input method and the individual input method, considering the potential kinetic constraints. Some C2 and C2+ hydrocarbons appear in the predicted gaseous products based on the three methods. The regional input method demonstrates that more H2 and CO are produced at higher temperature, which agrees with the experimental results. And more C2H4 and C2H2 release at higher temperature depending on the enhanced secondary gas cracking reactions. The peak concentration of every gas product is obtained at higher temperature with lower value compared to the experimental results possibly due to ignoring the effect of the shale ash. The individual input method indicates that C2 and C3 hydrocarbons are generated after the formation of CH4, CO, CO2 and H2. The change trends of CO2, CO and H2 obtained from the experiment and simulation with rising temperature are very similar, but those for CH4 are different, due to most likely certain limitations of a fixed bed reactor as a reaction system. Combining the HSC and PSR calculations, the obtained gas products are closer to the realistic situation.

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Acknowledgements

The authors express their gratitude to the State Key Laboratory of Heavy Oil Processing of China University of Petroleum for shale oil samples analysis and technical advice. This work was supported by the National Natural Science Foundation of China (Grant Nos. 50906051 and 51704194), Young Teacher Training Scheme of Shanghai Universities (Grant No. ZZGCD15062) and the Research Star-up Fund from Shanghai University of Engineering Science (Grant No. 2015-52).

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Authors and Affiliations

  1. Institute of Thermal Energy and Power Engineering, College of Mechanical Engineering, Shanghai University of Engineering Science, Shanghai, 201620, People’s Republic of China

    Sha Wang & Lizhi Song

  2. Institute of Thermal Energy Engineering, School of Mechanical Engineering, Shanghai Jiao Tong University, Shanghai, 200240, People’s Republic of China

    Xiumin Jiang

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Correspondence to Sha Wang.

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Wang, S., Song, L. & Jiang, X. Prediction of gaseous products from Dachengzi oil shale pyrolysis through combined kinetic and thermodynamic simulations. J Therm Anal Calorim 134, 1129–1144 (2018). https://doi.org/10.1007/s10973-018-7501-7

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