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Practices for modeling oil shale pyrolysis and kinetics

  • Muhammad Afzal Raja

    Muhammad Afzal Raja is currently completing his doctoral research at the Institute of Process Engineering, University of Chinese Academy of Sciences. His research areas include modeling oil shale pyrolysis and kinetics, process simulation and assessment of hydrogen and high-value hydrocarbon fuel products from oil shale pyrolysis. He served at Pakistan Oilfields Ltd. (May 2011–August 2013) and in Descon Integrated Projects Ltd. (August 2008–April 2013) as a process safety engineer. He received his graduation degree in 2007 from the University of Engineering and Technology, Lahore, Pakistan, and received his Master’s degree in 2009 from the University of Punjab, Pakistan. He has two presentations to his credit.

    , Yongsheng Zhao

    Yongsheng Zhao is currently completing his doctoral research at the Institute of Process Engineering, University of Chinese Academy of Sciences, and he will graduate in June 2017. His major is chemical engineering and technology. His research areas include ionic liquids for various gases absorption and separation: an extensive database with rich data and a systemic screening method. He has published seven SCI papers and one conference paper.

    , Xiangping Zhang

    Xiangping Zhang received her PhD degree in Chemical Engineering in 2002 from the Dalian University of Technology. Then she joined Institute of Process Engineering of CAS. Her research interests include process integration, thermodynamics and separation engineering. She has published about 130 papers in peer-reviewed journals, and obtained 20 issued Chinese invention patents and 4 issued PCT patents. She was awarded the National Award for Natural Sciences and the Nomination Award of the 4th Top Ten Outstanding Women in Chinese Academy of Sciences in 2012.

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    , Chunshan Li

    Chunshan Li received his PhD degree in Chemical Engineering from the Institute of Process Engineering in 2006. He was a postdoctoral fellow at Federal Institute for Materials Research and Testing, BAM (2006–2007), and a JSPS fellow at Nagoya University, Japan (2007–2009). He joined IPE, CAS and has been a professor at the Hundred Talents Project of IPE since September 2009. His research mainly focuses on a cleaner energy catalytic process, chemical synthesis, chemical process design and integration. He has published more than 70 peer-reviewed articles in journals such as AIChE J., Ind. Eng. Chem. Res. and Chem. Eng. J. and holds 29 patents.

    and Suojiang Zhang

    Suojiang Zhang is Professor and Director General of the Institute of Process Engineering (IPE), Chinese Academy of Sciences (CAS), a member of CAS, Director of Beijing Key Laboratory of Ionic Liquids Clean Process, and Director of Professional Committee of Chinese Chemical Society of Ionic Liquids and Green Engineering. He is “National Science Fund for Distinguished Young Scientists” Winner, 973 Chief Scientist, and fellow of the Royal Society of Chemistry. He mainly engages in ionic liquids and green process engineering. He has published more than 300 papers and more than 90 patents, and also edited or written four monographs. He won a number of awards, such as the Second Class Prize of National Natural Science Award in 2010.

Published/Copyright: March 17, 2017
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Abstract

Oil shale is one of the largest, relatively undeveloped natural fossil fuel resources in the world and so an important potential source of energy. The organic matter of oil shale is present as a complex combination of carbon, hydrogen, sulfur and oxygen named kerogen. Pyrolysis-gas chromatography-mass spectroscopy affords the opportunity to chemically characterize the main structural skeleton in this kerogen and is a favorable method to study the structural characteristics of kerogen at a molecular level. The thermal degradation of oil shale kerogen is a complex chemical process, accompanied by the wide variety of products obtained, which poses difficulties in the determination of the kinetics and mechanism of pyrolysis. Understanding the kinetics of kerogen decomposition to oil is critical to design a viable retorting process. Comprehensive kinetic data are also essential for accurate mathematical modeling of various oil shale processes. Classic graphical methods cannot unambiguously measure and estimate kinetic parameters due to the mathematical complexity. Advanced isoconversion methods would be appropriate for the calculation of the distribution of activation energies for multiple reactions involved in the decomposition of complex material such as kerogen to products. The range of variability in the principal activation energy is from about 200 to 242 kJ mol−1, with most samples being in the middle half of that range, while the range of frequency factors most likely in the 1012–1016 s−1 range, with most values within the middle half of that range. The review presents the complexity of the oil shale pyrolysis mechanism and pyrolysis kinetics along with the challenges in experimental procedures and modeling of oil shale pyrolysis kinetics.

About the authors

Muhammad Afzal Raja

Muhammad Afzal Raja is currently completing his doctoral research at the Institute of Process Engineering, University of Chinese Academy of Sciences. His research areas include modeling oil shale pyrolysis and kinetics, process simulation and assessment of hydrogen and high-value hydrocarbon fuel products from oil shale pyrolysis. He served at Pakistan Oilfields Ltd. (May 2011–August 2013) and in Descon Integrated Projects Ltd. (August 2008–April 2013) as a process safety engineer. He received his graduation degree in 2007 from the University of Engineering and Technology, Lahore, Pakistan, and received his Master’s degree in 2009 from the University of Punjab, Pakistan. He has two presentations to his credit.

Yongsheng Zhao

Yongsheng Zhao is currently completing his doctoral research at the Institute of Process Engineering, University of Chinese Academy of Sciences, and he will graduate in June 2017. His major is chemical engineering and technology. His research areas include ionic liquids for various gases absorption and separation: an extensive database with rich data and a systemic screening method. He has published seven SCI papers and one conference paper.

Xiangping Zhang

Xiangping Zhang received her PhD degree in Chemical Engineering in 2002 from the Dalian University of Technology. Then she joined Institute of Process Engineering of CAS. Her research interests include process integration, thermodynamics and separation engineering. She has published about 130 papers in peer-reviewed journals, and obtained 20 issued Chinese invention patents and 4 issued PCT patents. She was awarded the National Award for Natural Sciences and the Nomination Award of the 4th Top Ten Outstanding Women in Chinese Academy of Sciences in 2012.

Chunshan Li

Chunshan Li received his PhD degree in Chemical Engineering from the Institute of Process Engineering in 2006. He was a postdoctoral fellow at Federal Institute for Materials Research and Testing, BAM (2006–2007), and a JSPS fellow at Nagoya University, Japan (2007–2009). He joined IPE, CAS and has been a professor at the Hundred Talents Project of IPE since September 2009. His research mainly focuses on a cleaner energy catalytic process, chemical synthesis, chemical process design and integration. He has published more than 70 peer-reviewed articles in journals such as AIChE J., Ind. Eng. Chem. Res. and Chem. Eng. J. and holds 29 patents.

Suojiang Zhang

Suojiang Zhang is Professor and Director General of the Institute of Process Engineering (IPE), Chinese Academy of Sciences (CAS), a member of CAS, Director of Beijing Key Laboratory of Ionic Liquids Clean Process, and Director of Professional Committee of Chinese Chemical Society of Ionic Liquids and Green Engineering. He is “National Science Fund for Distinguished Young Scientists” Winner, 973 Chief Scientist, and fellow of the Royal Society of Chemistry. He mainly engages in ionic liquids and green process engineering. He has published more than 300 papers and more than 90 patents, and also edited or written four monographs. He won a number of awards, such as the Second Class Prize of National Natural Science Award in 2010.

Nomenclature
W0

Initial weight of the sample (mg)

Wt

Weight of the sample at time t (mg)

W

Weight of the sample at the end of the experiment (mg)

α

Conversion

β

Constant heating rate (°C min−1)

K*

Kerogen and bitumen originally present in oil shale

P

All volatilized products formed

B

All non-volatilized products

f1 and f2

Stoichiometric coefficients

t

Time

N

Number of heating rates

I

Integral symbol

Tα

Temperature at conversion α

R

Gas constant (8.314 kJ mol−1 K−1)

T

Temperature (K)

Tmax

Temperature of maximum reaction rate

E

Apparent activation energy (kJ mol−1)

Eα

Activation energy at conversion α

f(α)

Reaction model

f(T)

Temperature dependence of the reaction rate

Acknowledgments

This work was financially supported by the National Basic Research Program of China (2014CB744306), the National Natural Science Fund for Distinguished Young Scholars (21425625), and supported by the External Cooperation Program of B1C, Chinese Academy of Sciences (122111KYS820150017) and the National Project of International Cooperation (2013DFG62640).

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Received: 2016-9-5
Accepted: 2016-12-23
Published Online: 2017-3-17
Published in Print: 2017-12-20

©2018 Walter de Gruyter GmbH, Berlin/Boston

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