Journal of Thermal Analysis and Calorimetry

, Volume 126, Issue 3, pp 1679–1688 | Cite as

A new method for determining average boiling points of oils using a thermogravimetric analyzer

Application to unconventional oil fractions
  • Rivo Rannaveski
  • Oliver Järvik
  • Vahur Oja


A new alternative experimental method is proposed to determine mass average boiling points (WABP) of oils with narrow boiling ranges. The method was developed to evaluate the atmospheric boiling points of unconventional oil fractions in a convenient and fast manner while using only a small amount of sample (<20 mg). The method is based on conversion of the differential mass loss curve from thermogravimetric analysis (TG) into a boiling (or condensation) curve of the vaporized species (narrow fractions as pseudocomponents). From the latter, the WABP is then calculated. The differential mass loss curve is measured during the vaporization of oil through a pinhole with a diameter of 50 µm. In this regard, the method is similar to the approach used in the ASTM E1782 standard (Standard Test Method for Determining Vapor Pressure by Thermal Analysis). The fractions used to develop the method were obtained from rectification of a shale oil that was rich in phenolic compounds. For evaluation of the results, the average boiling points calculated from TG were compared with the average boiling point values (TBP) obtained from rectification results (calculated as the average of the initial and final temperatures of the cut). For evaluating the method’s accuracy, 17 fractions with narrow boiling ranges (boiling ranges from 5 to 20 °C) and 12 wider fractions (boiling ranges from 20 to 56 °C), that were obtained by combining the closest narrow fractions, were used. The average deviation of the boiling points calculated using this TG method was 0.8 °C (absolute average deviation 1.9 °C), and the maximum deviation was 4.5 °C (with only 2 points deviating from the TBP values more than 4 °C).


Thermogravimetry Narrow boiling range fraction Average boiling point Unconventional oil Shale oil 

List of symbols


Mass-, volume- or molar average boiling point of the mixture (°C)


Respectively the mass-, volume- or mole fraction of component i, j, k


Rate of mass loss (mg min−1)



Support for the study was provided by National R&D program “Energy” under the Project AR10129 “Examination of the Thermodynamic Properties of Relevance to the Future of the Oil Shale Industry”. The authors also acknowledge financial support provided by the Republic of Estonia Ministry of Education and Research, under target financing SF0140022s10 and under Estonian Scientific Foundation Grant 9297. For revising the language of the manuscript, the authors thank colleague Mr. Zachariah Steven Baird.


  1. 1.
    Smith RL, Watson KM. Boiling points and critical properties of hydrocarbon mixtures. Ind Eng Chem. 1937;29:1408–14.CrossRefGoogle Scholar
  2. 2.
    Riazi MR. Characterization and properties of petroleum fractions. 1st ed. West Conshohocken: ASTM; 2005.CrossRefGoogle Scholar
  3. 3.
    McKetta JJ. Encyclopedia of chemical processing and design. Petroleum fractions properties to phosphoric acid plants: alloy selection, vol. 35. New York: CRC Press; 1990.Google Scholar
  4. 4.
    Edmister WC, Lee BI. Applied hydrocarbon thermodynamics, vol. 1. Houston: Gulf Publishing Company; 1984.Google Scholar
  5. 5.
    Wauquier JP. Petroleum refining. Crude oil, petroleum products, process flowsheets, vol. 1. Paris: Editions Technip; 1995.Google Scholar
  6. 6.
    ASTM D2892-15. Standard test method for distillation of crude petroleum (15-theoretical plate column). West Conshohocken: ASTM International; 2015.Google Scholar
  7. 7.
    ASTM D1160-15. Standard test method for distillation of petroleum products at reduced pressure. West Conshohocken: ASTM International; 2015.Google Scholar
  8. 8.
    ASTM D86-12. Standard test method for distillation of petroleum products at atmospheric pressure. West Conshohocken: ASTM International; 2012.Google Scholar
  9. 9.
    Hu Z, Li L, Shui Y. Thermogravimetric analysis of fuel film evaporation. Chin Sci Bull. 2006;51:2050–7.CrossRefGoogle Scholar
  10. 10.
    Mondragon F, Ouchi K. New method of obtaining the distillation curves of petroleum products and coal-derived liquids using a small amount of sample. Fuel. 1984;63:61–5.CrossRefGoogle Scholar
  11. 11.
    Li F, Chang LP, Wen P, Xie KC. Simulated distillation of coal tar. Energy Sources. 2001;23:189–99.CrossRefGoogle Scholar
  12. 12.
    ASTM E1782-14. Standard test method for determining vapor pressure by thermal analysis. West Conshohocken: ASTM International; 2014.Google Scholar
  13. 13.
    Siitsman C, Oja V. Extension of the DSC method to measuring vapor pressures of narrow boiling range oil cuts. Thermochim Acta. 2015;622:31–7.CrossRefGoogle Scholar
  14. 14.
    Goodrum JW, Siesel EM. Thermogravimetric analysis for boiling points and vapor pressure. J Therm Anal. 1996;46:1251–8.CrossRefGoogle Scholar
  15. 15.
    Goodrum JW. Volatility and boiling points of biodiesel from vegetable oils and tallow. Biomass Bioenergy. 2002;22:205–11.CrossRefGoogle Scholar
  16. 16.
    Dawar R, Jain A, Babu R, Ananthasivan K, Anthonysamy S. Thermodynamic characterization of Fe2TeO6. J Therm Anal Calorim. 2015;122:885–91.CrossRefGoogle Scholar
  17. 17.
    Järvik O, Rannaveski R, Roo E, Oja V. Evaluation of vapor pressures of 5-methylresorcinol derivatives by thermogravimetric analysis. Thermochim Acta. 2014;590:198–205.CrossRefGoogle Scholar
  18. 18.
    Opik I, Golubev N, Kaidalov A, Kann J, Elenurm A. Current status of oil shale processing in solid heat carrier UTT (Galoter) retorts in Estonia. Oil Shale. 2001;18:99–108.Google Scholar
  19. 19.
    Savest N, Oja V, Kaevand T, Lille Ü. Interaction of Estonian Kukersite with organic solvents: a volumetric swelling and molecular simulation study. Fuel. 2007;86:17–21.CrossRefGoogle Scholar
  20. 20.
    Hruljova J, Savest N, Oja V, Suuberg E. Kukersite oil shale kerogen solvent swelling in binary mixtures. Fuel. 2013;105:77–82.CrossRefGoogle Scholar
  21. 21.
    Oja V. Is It time to improve the status of oil shale science. Oil Shale. 2007;24:97–9.Google Scholar
  22. 22.
    Oja V, Suuberg E. Oil shale processing, chemistry and technology. Fossil energy: selected entries from the encyclopedia of sustainability science and technology. New York: Springer; 2013. p. 99–148.Google Scholar
  23. 23.
    Lille Ü. Current knowledge on the origin and structure of Estonian Kukersite Kerogen. Oil Shale. 2003;20:53–63.Google Scholar
  24. 24.
    Baird ZS, Oja V, Järvik O. Distribution of hydroxyl groups in Kukersite shale oil: quantitative determination using Fourier transform infrared (FT-IR) spectroscopy. Appl Spectrosc. 2015;69:555–62.CrossRefGoogle Scholar
  25. 25.
    Gierycz P, Gregorowicz J, Malanowski S. Vapor pressures and excess Gibbs energies of (butan-1-ol + n-octane or n-decane) at 373.15 and 383.15 K. J Chem Thermodyn. 1988;20:385.CrossRefGoogle Scholar
  26. 26.
    Éigenson AS. Regularity in boiling point distribution of crude oil fractions. Chem Tech Fuel Oil+. 1973;9:3–8.CrossRefGoogle Scholar
  27. 27.
    Oja V. Characterization of tars from Estonian Kukersite oil shale based on their volatility. J Anal Appl Pyrolysis. 2005;74:55–60.CrossRefGoogle Scholar
  28. 28.
    Daubert TE. Petroleum fraction distillation interconversions. Hydrocarb Process. 1994;73:75–8.Google Scholar
  29. 29.
    Riazi MR, Daubert TE. Analytical correlations interconvert distillation curve types. Oil Gas J. 1986;84:50–7.Google Scholar
  30. 30.
    Huang H, Wang K, Wang S, Klein MT, Calkins WH. Distillation of liquid fuels by thermogravimetry. Prepr Pap Am Chem Soc Div Fuel Chem. 1996;41:87–92.Google Scholar

Copyright information

© Akadémiai Kiadó, Budapest, Hungary 2016

Authors and Affiliations

  1. 1.Department of Chemical EngineeringTallinn University of Technology (TUT)TallinnEstonia

Personalised recommendations