Skip to main content
SpringerLink
Log in

Structural characterization of thermal bitumen extracted from Fushun oil shale semi-coke with ionic liquid/N-methyl pyrrolidone

  • Published:
Journal of Thermal Analysis and Calorimetry Aims and scope Submit manuscript

Abstract

Thermal bitumen is an organic intermediate during the pyrolysis of oil shale kerogen. In this work, semi-cokes were prepared for obtaining thermal bitumen by pyrolyzing Fushun oil shale to 400–500 °C, followed by extraction with a mixture of an ionic liquid (1-butyl-3-methylimidazolium chloride) and a polar solvent (N-methyl pyrrolidone). The critical thermal bitumen with the highest yield of the 450 °C semi-coke extraction was carefully performed by gas chromatography–mass spectrometry, Fourier transform infrared spectrophotometry, liquid-state 13C nuclear magnetic resonance spectroscopy, and X-ray photoelectron spectroscopy. The thermal bitumen was mainly composed of aliphatic structures, especially methylene chains. The dominant aliphatic hydrocarbons were between C13 and C27, and the alkanes and corresponding alkenes from C14 to C22 were continuously identified in pairs. A small quantity of benzenes and naphthalenes was identified as well as phenols, carboxylic acids, and nitrogen compounds. The oxygen functional groups were mainly carbon and oxygen double bonds, and the nitrogen and sulfur functional groups were characterized as pyrrole and thiophene. Ultimately, a structural formula (C370H570O29N4S) and its atomic distribution were proposed, based on the final analysis of experimental data.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8

Similar content being viewed by others

References

  1. Li SY, Qian JL, Qin KZ, Zhu YJ. Study on the kinetics of oil shale pyrolysis with bitumen as an intermediate product. J Fuel Chem Technol. 1987;02:118–23.

    Google Scholar 

  2. Wen CS, Kobylinski TP. Low-temperature oil shale conversion. Fuel. 1983;62(11):1269–73.

    Article  CAS  Google Scholar 

  3. Miknis FP, Lindner AW, Gannon AJ, Davis MF, Maciel GE. Solid state 13C NMR studies of selected oil shales from Queensland, Australia. Org Geochem. 1984;7(3–4):239–48.

    Article  CAS  Google Scholar 

  4. Putun E, Akar A, Ekinci E, Bartle KD. Chemistry and geochemistry of Turkish oil shale kerogens. Fuel. 1988;67(8):1106–10.

    Article  CAS  Google Scholar 

  5. Rio JC, Molla JG, Vila FJ, Martin F. Composition and origin of the aliphatic extractable hydrocarbons in the Puertollano (Spain) oil shale. Org Geochem. 1994;21(8–9):897–909.

    Google Scholar 

  6. Siskin M, Scouten CG, Rose KD, Aczel T, Pabst RE. Detailed structural characterization of the organic material in Rundle Ramsay crossing and Green River oil shales. Fuel Energy Abstr. 1996;37(1):10.

    Google Scholar 

  7. Qin KZ, Lao YX. Investigation on the constitution and the structure of Maoming and Fushun oil shales. J Fuel Chem Technol. 1985;13(2):133–40.

    CAS  Google Scholar 

  8. Wang Q, Huang ZY, Shi JX, Wang ZC, Sui Y. Chemical structure analysis of oil shale kerogen. CIESC J. 2015;66(05):1861–6.

    CAS  Google Scholar 

  9. Orendt AM, Pimienta ISO, Badu SR, Solum MS, Pugmire RJ, Facelli JC. Three-dimensional structure of the Siskin Green River oil shale kerogen model: a comparison between calculated and observed properties. Energy Fuels. 2013;27(2):702–10.

    Article  CAS  Google Scholar 

  10. Ungerer P, Collell J, Yiannourakou M. Molecular modeling of the volumetric and thermodynamic properties of kerogen: influence of organic type and maturity. Energy Fuels. 2015;29(1):91–105.

    Article  CAS  Google Scholar 

  11. Zhang Z, Jamili A. Modeling the kerogen 3D molecular structure. In: Society of petroleum engineers SPE/CSUR unconventional resources conference (2015-10-20).

  12. Wang Q, Pan S, Bai JR, Chi MS, Cui D, Wang ZC, Liu Q, Xu F. Experimental and dynamics simulation studies of the molecular modeling and reactivity of the Yaojie oil shale kerogen. Fuel. 2018;230:319–30.

    Article  CAS  Google Scholar 

  13. Shi J, Ma Y, Li SY, Wu J, Zhu YK, Teng J. Characteristics of Estonian oil shale kerogen and its pyrolysates with thermal bitumen as a pyrolytic intermediate. Energy Fuels. 2017;31(5):4808–16.

    Article  CAS  Google Scholar 

  14. Shi J, Ma Y, Li S, Zhang L. Characteristics of thermal bitumen structure as the pyrolysis intermediate of Longkou oil shale. Energy Fuels. 2017. https://doi.org/10.1021/acs.energyfuels.7b01542.

    Article  Google Scholar 

  15. Li Q, Han X, Liu Q, Jiang X. Thermal decomposition of Huadian oil shale. Part 1. Critical organic intermediates. Fuel. 2014;121(2):109–16.

    Article  CAS  Google Scholar 

  16. Blanchard LA, Hancu D, Beckman EJ, Brennecke JF. Green processing using ionic liquids and CO2. Nature. 1999;399(6731):28–9.

    Article  Google Scholar 

  17. Jiang W, Zhu W, Chang Y, Chao Y, Li H. Ionic liquid extraction and catalytic oxidative desulfurization of fuels using dialkylpiperidinium tetrachloroferrates catalysts. Chem Eng J. 2014;250:48–54.

    Article  CAS  Google Scholar 

  18. Brandt A, Grasvik J, Hallett JP, Welton T. Deconstruction of lignocellulosic biomass with ionic liquids. Green Chem. 2013;15(3):550.

    Article  CAS  Google Scholar 

  19. Sonmez O, Yildiz O, Cakir MO, Gozmen B, Giray ES. Influence of the addition of various ionic liquids on coal extraction with NMP. Fuel. 2018;212:12–8.

    Article  CAS  Google Scholar 

  20. Sui H, Zhang J, Yuan Y, He L, Bai Y, Li X. Role of binary solvent and ionic liquid in bitumen recovery from oil sands. Can J Chem Eng. 2016;94(6):1191–6.

    Article  CAS  Google Scholar 

  21. Han H, Zhong NN, Huang CX, Zhang W. Pyrolysis kinetics of oil shale from Northeast China: implications from thermogravimetric and rock-eval experiments. Fuel. 2015;159:776–83.

    Article  CAS  Google Scholar 

  22. Ma Z, Sun Q, Ye J, Yao Q, Zhao C. Study on the thermal degradation behaviors and kinetics of alkali lignin for production of phenolic-rich bio-oil using TGA-FTIR and Py-GC/MS. J Anal Appl Pyrol. 2016;117:116–24.

    Article  CAS  Google Scholar 

  23. Kelemen SR, Afeworki M, Gorbaty ML, Sansone M, Pugmire RJ. Direct characterization of kerogen by X-ray and solid-state 13C nuclear magnetic resonance methods. Energy Fuels. 2008;21(3):1548–61.

    Article  Google Scholar 

  24. Wang Q, Liu Q, Wang ZC, Liu HP, Bai JR, Ye JB. Characterization of organic nitrogen and sulfur in the oil shale kerogens. Fuel Process Technol. 2017;160:70–177.

    Article  Google Scholar 

  25. Ma LL, Qin ZH, Zhang L, Liu X, Chen H. Peak fitting methods and parameter settings in XPS analysis for organic sulfur in coal. J Fuel Chem Technol. 2014;42(03):277–83.

    CAS  Google Scholar 

  26. Tian DM, Liu XY, Ding MJ. CS2 extraction and FTIR/GCMS analysis of a Chinese brown coal. Min Sci Technol. 2010;20(4):562–5.

    CAS  Google Scholar 

  27. Biller P, Ross AB, Skill SC. Investigation of the presence of an aliphatic biopolymer in cyanobacteria: implications for kerogen formation. Org Geochem. 2015;33:64–9.

    Article  Google Scholar 

  28. You Y, Han X, Liu J, Jiang X. Structural characteristics and pyrolysis behaviors of huadian oil shale kerogens using solid-state 13C NMR, Py-GCMS and TG. J Therm Anal Calorim. 2017;131:1845–55.

    Article  Google Scholar 

  29. Craddock PR, Le Doan TV, Bake K, Polyakov M, Charsky AM, Pomerantz AE. Evolution of kerogen and bitumen during thermal maturation via semi-open pyrolysis investigated by infrared spectroscopy. Energy Fuels. 2015;29(4):2197–210.

    Article  CAS  Google Scholar 

  30. Nie F, He D, Guan J, Bao H, Zhang K, Meng T, Zhang Q. Influence of temperature on products distribution during indonesian oil sand fast pyrolysis and the relations of products to the oil sand organic structure. Energy Fuels. 2017;31:1318–28.

    Article  CAS  Google Scholar 

  31. Shinn JH. From coal to single-stage and two-stage products: a reactive model of coal structure. Fuel. 1984;63:1187–96.

    Article  CAS  Google Scholar 

  32. Lille U, Heinmaa I, Pehk T. Molecular model of Estonian Kukersite kerogen evaluated by 13C MAS NMR spectra. Fuel. 2003;82:799–804.

    Article  CAS  Google Scholar 

  33. Tong J, Han X, Wang S, Jiang X. Evaluation of structural characteristics of Huadian oil shale kerogen using direct techniques (solid-state 13C NMR, XPS, FT-IR, and XRD). Energy Fuels. 2011;25(25):4006–13.

    Article  CAS  Google Scholar 

  34. Kelemen SR, Afeworki M, Gorbaty ML, Kwiatek PJ, Solum MS, Hu JZ, Pugmire RJ. XPS and 15N NMR study of nitrogen forms in carbonaceous solids. Energy Fuels. 2002;16(6):1507–15.

    Article  CAS  Google Scholar 

  35. Mushrush GW, Beal EJ, Hardy DR, Hughes JM. Nitrogen compound distribution in middle distillate fuels derived from petroleum, oil shale, and tar sand sources. Fuel Process Technol. 1999;61:197–210.

    Article  CAS  Google Scholar 

  36. Huang L, Ning ZF, Wang Q, Ye HT, Wang ZZ, Sun Z, Qin HB. Microstructure and adsorption properties of organic matter in Chinese cambrian gas shale: experimental characterization, molecular modeling and molecular simulation. Coal Geol. 2018;198:14–28.

    Article  CAS  Google Scholar 

  37. Pan S, Wang Q, Bai JR, Chi MS, Cui D, Wang ZC, Liu Q. Molecular structure and electronic properties of oil shale kerogen: an experimental and molecular modeling study. Energy Fuels. 2018;32(12):12394–404.

    Article  CAS  Google Scholar 

  38. Guan XH, Liu Y, Wang D, Wang Q, Chi MS, Liu S. Three-dimensional structure of a Huadian oil shale kerogen model: an experimental and theoretical study. Energy Fuels. 2015;29(7):4122–36.

    Article  CAS  Google Scholar 

  39. Ru X, Cheng Z, Song L. Experimental and computational studies on the average molecular structure of Chinese Huadian oil shale kerogen. J Mol Struct. 2012;1030:10–8.

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (No. 51676032 and No. 51776032), the Program for Changjiang Scholars and Innovative Research Team in University (IRT13052), and the Science and Technology Innovation and Development Projects of Jilin City (20166006).

Author information

Authors and Affiliations

  1. State Key Laboratory of Heavy Oil Processing, College of Science, China University of Petroleum (Beijing), Beijing, 102249, People’s Republic of China

    Haoshu Ding, Yue Ma & Shuyuan Li

  2. School of Energy and Power Engineering, Northeast Electric Power University, Jilin City, 132012, Jilin, People’s Republic of China

    Haoshu Ding, Qing Wang, Wenpeng Hong & Ming Jiang

Authors
  1. Haoshu Ding
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Yue Ma
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Shuyuan Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Qing Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Wenpeng Hong
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Ming Jiang
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Yue Ma.

Ethics declarations

Conflict of interest

The authors declare no competing financial interest.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Ding, H., Ma, Y., Li, S. et al. Structural characterization of thermal bitumen extracted from Fushun oil shale semi-coke with ionic liquid/N-methyl pyrrolidone. J Therm Anal Calorim 146, 1613–1622 (2021). https://doi.org/10.1007/s10973-020-10135-w

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10973-020-10135-w

Keywords

Search

Navigation