Journal of Thermal Analysis and Calorimetry

, Volume 124, Issue 3, pp 1661–1670 | Cite as

Kinetic modeling of deoiled asphaltene particle pyrolysis in thermogravimetric analysis

  • Yan Cheng
  • Binhang Yan
  • Tianyang Li
  • Yi Cheng


The pyrolysis behavior of deoiled asphaltene particles was experimentally studied by thermogravimetric analysis. Considering that the activation energy would change with the evolution of pyrolysis reactions, a modified competition model was proposed to appropriately describe the pyrolysis kinetics. The model parameters were fitted with experimental results. Compared with the original two-stage model, the modified competition model showed the capability of predicting the asphaltene pyrolysis at various heating conditions using fixed kinetic parameters. The results exhibited that the modified competition model can well simulate the asphaltene pyrolysis in the main mass loss temperature range from 500 to 900 K as well as the slow decomposition at the temperatures greater than 900 K during the devolatilization process of asphaltene particles at hundred micrometer size. The modified competition model was further coupled with a heat transfer model at particle scale, including the heat exchange between the particle and the surrounding atmosphere as well as the heat transfer inside the particle. It is found that during the thermogravimetric analysis, the particle surface temperature was close to that of atmosphere, and the heat transfer effect inside the particle could be ignored for hundred-micron-sized particles. However, the temperature gradient inside particles should be considered for millimeter-sized particles. Thus, the particle samples should be sieved to hundred micron sized or smaller when studying the basic pyrolysis behaviors in order to acquire kinetic parameters for asphaltene pyrolysis by thermogravimetric analysis.


Asphaltene Pyrolysis kinetics Thermogravimetric analysis Single-particle modeling 



Financial supports from the National Basic Research Program of China (973 Program No. 2012CB720301) and the National Science and Technology Key Supporting Project (2013BAF08B04), PetroChina Innovation Foundation (2013D-5006-0508) are acknowledged.


  1. 1.
    Chen K, Wang ZX, Liu H, Ruan YJ, Guo AJ. Thermodynamic and thermokinetic study on pyrolysis process of heavy oils. J Therm Anal Calorim. 2013;112(3):1423–31.CrossRefGoogle Scholar
  2. 2.
    McCants MT. Method for production of hydrocarbon diluent from heavy crude oil. U.S. Patent 5,109,928; 1992.Google Scholar
  3. 3.
    Lee JM, Shin S, Ahn S, Chun JH, Lee KB, Mun S, et al. Separation of solvent and deasphalted oil for solvent deasphalting process. Fuel Process Technol. 2014;119:204–10.CrossRefGoogle Scholar
  4. 4.
    Mutyala S, Fairbridge C, Pare JRJ, Belanger JMR, Ng S, Hawkins R. Microwave applications to oil sands and petroleum: a review. Fuel Process Technol. 2010;91(2):127–35.CrossRefGoogle Scholar
  5. 5.
    Gieg LM, Duncan KE, Suflita JM. Bioenergy production via microbial conversion of residual oil to natural gas. Appl Environ Microbiol. 2008;74(10):3022–9.CrossRefGoogle Scholar
  6. 6.
    Rana MS, Samano V, Ancheyta J, Diaz JAI. A review of recent advances on process technologies for upgrading of heavy oils and residua. Fuel. 2007;86(9):1216–31.CrossRefGoogle Scholar
  7. 7.
    Marchionna M, Delbianco A, Panariti N, Montanari R, Rosi S, Correra S. The combined use of three process units: hydroconversion with catalysts in slurry phase, distillation or flash, deasphalting is characterized in that the three units operate on mixed streams; catalyst reuse; receptivity; stability; quality. U.S. Patent Application 10/188,785; 2002.Google Scholar
  8. 8.
    Feng L, Mao Y, Wang J, Wang J, Zhang G. Effect of operating parameters on the performance of a new spray granulation tower. Resources, environment and engineering. London: CRC Press; 2014. p. 271.Google Scholar
  9. 9.
    Avid B, Purevsuren B, Born M, Dugarjav J, Davaajav Y, Tuvshinjargal A. Pyrolysis and TG analysis of Shivee Ovoo coal from Mongolia. J Therm Anal Calorim. 2002;68(3):877–85.CrossRefGoogle Scholar
  10. 10.
    Wen WY, Cain E. Catalytic pyrolysis of a coal-tar in a fixed-bed reactor. Ind Eng Chem Proc DD. 1984;23(4):627–37.CrossRefGoogle Scholar
  11. 11.
    Stenseng M, Jensen A, Dam-Johansen K. Investigation of biomass pyrolysis by thermogravimetric analysis and differential scanning calorimetry. J Anal Appl Pyrol. 2001;58:765–80.CrossRefGoogle Scholar
  12. 12.
    Kok MV. Simultaneous thermogravimetry–calorimetry study on the combustion of coal samples: effect of heating rate. Energy Convers Manag. 2012;53(1):40–4.CrossRefGoogle Scholar
  13. 13.
    Ozbas KE, Hicyilmaz C, Kok MV, Bilgen S. Effect of cleaning process on combustion characteristics of lignite. Fuel Process Technol. 2000;64(1–3):211–20.CrossRefGoogle Scholar
  14. 14.
    Kok MV. Coal pyrolysis: thermogravimetric study and kinetic analysis. Energy Sources. 2003;25(10):1007–14.CrossRefGoogle Scholar
  15. 15.
    Jia H, Zhao JZ, Pu WF, Zhao J, Kuang XY. Thermal study on light crude oil for application of high-pressure air injection (HPAI) process by TG/DTG and DTA tests. Energy Fuel. 2012;26(3):1575–84.CrossRefGoogle Scholar
  16. 16.
    Jia H, Zhao JZ, Pu WF, Liao R, Wang LL. The influence of clay minerals types on the oxidation thermokinetics of crude oil. Energy Sources Part A Recov Util Environ Effects. 2012;34(10):877–86.CrossRefGoogle Scholar
  17. 17.
    Vossoughi S, Willhite G, Elshoubary Y, Bartlett G. Study of the clay effect on crude-oil combustion by thermogravimetry and differential scanning calorimetry. J Therm Anal. 1983;27(1):17–36.CrossRefGoogle Scholar
  18. 18.
    Yue C, Watkinson A. Pyrolysis of pitch. Fuel. 1998;77(7):695–711.CrossRefGoogle Scholar
  19. 19.
    Gong JS, Fu WB, Zhong BJ. A study on the pyrolysis of asphalt. Fuel. 2003;82(1):49–52.CrossRefGoogle Scholar
  20. 20.
    Altun NE, Hicyilmaz C, Kok MV. Effect of particle size and heating rate on the pyrolysis of Silopi asphaltite. J Anal Appl Pyrol. 2003;67(2):369–79.CrossRefGoogle Scholar
  21. 21.
    Tonbul Y, Saydut A, Hamamci C. Pyrolysis kinetics of asphaltites determined by thermal analysis. Oil Shale. 2006;23(3):286–93.Google Scholar
  22. 22.
    Zhang Q, Li QF, Zhang LX, Fang YT, Wang ZQ. Experimental and kinetic investigation of the pyrolysis, combustion, and gasification of deoiled asphalt. J Therm Anal Calorim. 2014;115(2):1929–38.CrossRefGoogle Scholar
  23. 23.
    Shin Y, Choi S, Ahn DH. Pressurized drop tube furnace tests of global coal gasification characteristics. Int J Energy Res. 2000;24(9):749–58.CrossRefGoogle Scholar
  24. 24.
    Yan BH, Cheng Y, Cheng Y. Particle-scale modeling of coal devolatilization behaviors for coal pyrolysis in thermal plasma reactors. AIChE J. 2015;61(3):913–21.CrossRefGoogle Scholar
  25. 25.
    Liu ML, Mao Y, Wang JY, Wang J, Sun XW, Xu CM. Effect of swirl on hydrodynamics and separation performance of a spray granulation tower with array nozzles. Powder Technol. 2012;227:61–6.CrossRefGoogle Scholar
  26. 26.
    Manya JJ, Velo E, Puigjaner L. Kinetics of biomass pyrolysis: a reformulated three-parallel-reactions model. Ind Eng Chem Res. 2003;42(3):434–41.CrossRefGoogle Scholar
  27. 27.
    Kobayashi H, Howard J, Sarofim AF. Coal devolatilization at high temperatures. Symp (Int) Combust. 1977;16(1):411–25.CrossRefGoogle Scholar
  28. 28.
    Bliek A, Vanpoelje WM, Vanswaaij WPM, Vanbeckum FPH. Effects of intraparticle heat and mass-transfer during devolatilization of a single coal particle. AIChE J. 1985;31(10):1666–81.CrossRefGoogle Scholar
  29. 29.
    Miura K. Mild conversion of coal for producing valuable chemicals. Fuel Process Technol. 2000;62(2–3):119–35.CrossRefGoogle Scholar
  30. 30.
    Saikia BK, Boruah RK, Gogoi PK, Baruah BP. A thermal investigation on coals from Assam (India). Fuel Process Technol. 2009;90(2):196–203.CrossRefGoogle Scholar
  31. 31.
    Cheng Y, Yan BH, Li TY, Cheng Y, Li X, Guo CY. Experimental study on coal tar pyrolysis in thermal plasma. Plasma Chem Plasma Process. 2015;35(2):401–13.CrossRefGoogle Scholar
  32. 32.
    Rohsenow WM, Hartnett JP, Cho YI. Handbook of heat transfer. New York: McGraw-Hill; 1998.Google Scholar
  33. 33.
    Spalding DB. Some fundamentals of combustion. London: Butterworths; 1955.Google Scholar
  34. 34.
    Versteeg HK, Malalasekera W. An introduction to computational fluid dynamics: the finite method. New Jersey: Prentice Hall; 1995.Google Scholar

Copyright information

© Akadémiai Kiadó, Budapest, Hungary 2016

Authors and Affiliations

  1. 1.Department of Chemical EngineeringTsinghua UniversityBeijingPeople’s Republic of China

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