Pyrolysis in Semi-Open Systems



Effects of pressure on product transport and enhanced secondary reactions are described, including simple ways of modeling them and the beneficial effect of H2. Fractionation of molecular types during vaporization is summarized. Cracking kinetics for oil and model compounds are reviewed. Nearly all results are consistent with an effective activation energy of 56–60 kcal/mol, although a higher energy may be appropriate at the low temperatures and higher pressures associated with cracking in the subsurface. The consequences of ignoring isoconversional character are described.


Coal pyrolysis Coal hydrogenation Direct coal liquefaction Oil shale Effective activation energy DAEM Partition coefficient Kerogen decomposition Oil cracking Oil coking 


  1. 1.
    D.B. Anthony, J.B. Howard, H.C. Hottel, Rapid devolatilization of pulverized coal, in Fifteenth Symposium International on Combustion, The Combustion Institute, Pittsburgh, 1303–1317 1975Google Scholar
  2. 2.
    T.F. Wall, G.-S. Liu, H.-W. Wu, D.G. Roberts, K.K. Benfall, S. Gupta, J.A. Lucas, D.J. Harris, Effects of pressure on coal reactions during pulverized coal combustion and gasification. Prog. Energy Combust. Sci. 28, 405–433 (2002)CrossRefGoogle Scholar
  3. 3.
    E.M. Suuberg, W.A. Peters, J.B. Howard, Product compositions and formation kinetics in rapid pyrolysis of pulverized coal—implications for combustion, in Seventeenth Symposium International on Combustion, The Combustion Institute, Pittsburgh, 117–130 1979Google Scholar
  4. 4.
    P.R. Solomon, D.G. Hamblen, R.M. Carangelo, M.A. Serio, G.V. Deshpande, General model of coal devolatilization. Energy Fuels 2, 405–422 (1988)CrossRefGoogle Scholar
  5. 5.
    A.K. Burnham, R.L. Braun, General kinetic model of oil shale pyrolysis. Situ 9, 1–23 (1985)Google Scholar
  6. 6.
    A.K. Burnham, Chemistry of shale oil cracking, in Oil Shale, Tar Sands, and Related Materials, ACS Symposium Series 163, American Chemical Society, 39–60 1981, ed. by H.C. StaufferGoogle Scholar
  7. 7.
    E.R. Bissell, A.K. Burnham, R.L. Braun, Shale oil cracking kinetics and diagnostics. Ind. Eng. Chem. Proc. Des. Devel. 24, 381–386 (1985)CrossRefGoogle Scholar
  8. 8.
    M.A. Serio, W.A. Peters, J.B. Howard, Kinetics of vapor-phase secondary reactions of prompt coal pyrolysis tars. Ind. Eng. Chem. Res. 26, 1831–1838 (1987)CrossRefGoogle Scholar
  9. 9.
    M.-S Oh, W.A. Peters, J.B. Howard, An experimental and modeling study of softening coal pyrolysis. AICHE J. 35, pp. 775–792 (1989)Google Scholar
  10. 10.
    P.R. Solomon, T.H. Fletcher, R.J. Pugmire, Progress in coal pyrolysis. Fuel 72, 587–597 (1993)CrossRefGoogle Scholar
  11. 11.
    J.R. Gibbins, R. Kandiyoti, The effect of variations in time-temperature history on product distribution from coal pyrolysis. Fuel 68, 895–903 (1989)CrossRefGoogle Scholar
  12. 12.
    J.R. Gibbins, R. Kandiyoti, Experimental study of coal pyrolysis and hydropyrolysis at elevated pressures using a variable heating rate wire-mesh apparatus. Energy Fuels 3, 670–677 (1989)CrossRefGoogle Scholar
  13. 13.
    A.K. Burnham, A simple kinetic model of oil generation, vaporization, coking, and cracking. Energy Fuels 29, 7156–7167 (2015). Correction: Energy Fuels 30, 2524–2524 (2016)Google Scholar
  14. 14.
    P.R. Solomon, M.A. Serio, R.M. Carangelo, J.R. Markham, Very rapid coal pyrolysis. Fuel 65, 182–194 (1986)CrossRefGoogle Scholar
  15. 15.
    C.W. Lee, A.W. Scaroni, R.G. Jenkins, Effect of pressure on the devolatilization and swelling behavior of a softening coal during rapid heating. Fuel 70, 957–965 (1991)CrossRefGoogle Scholar
  16. 16.
    P.R. Solomon, T.H. Fletcher, Impact of coal pyrolysis on combustion, Twenty-Fifth Symposium International on Combustion, The Combustion Institute, Pittsburgh, pp. 463–474 (1994)Google Scholar
  17. 17.
    S. Niksa, FLASHCHAIN theory for rapid coal devolatilization kinetics. 5. Interpreting rates of devolatilization for various coal types and operating conditions. Energy Fuels 8, 671–679 (1994)CrossRefGoogle Scholar
  18. 18.
    A.K. Burnham, J.J. Sweeney, A chemical kinetic model of vitrinite maturation and reflectance. Geochim. Cosmochim. Acta 53, 2649–2657 (1989)CrossRefGoogle Scholar
  19. 19.
    D.W. van Krevelen, Coal—Topology, Chemistry, Physics, Constitution,Chap. 23 (Elsevier, 1993) pp. 699–701Google Scholar
  20. 20.
    P.F. Britt, W.S. Mungall, A.C. Buchanan III, Pyrolysis of a polymeric model of aromatic carboxylic acids in low—rank coal. Energy Fuels 12, 660–661 (1998)CrossRefGoogle Scholar
  21. 21.
    M.S. Serio, P.R. Solomon, E. Kroo, R. Bassilakis, R. Mallhotra, D. McMillen, Studies of coal pretreatment in direct liquefaction. Prep. ACS Div. Fuel Chem. 35(1), 61–69 (1990)Google Scholar
  22. 22.
    J.R. Gibbins, Z.S. Gonenc, R. Kandiyoti, Pyrolysis and hydropyrolysis of coal: comparison of product distributions from a wire-mesh and hot-rod reactor. Fuel 70, 621–626 (1991)CrossRefGoogle Scholar
  23. 23.
    K.K. Robinson, Reaction engineering of direct coal liquefaction. Energies 2, 976–1006 (2009)CrossRefGoogle Scholar
  24. 24.
    S. Vasireddy, B. Morreale, A. Cugini, C. Song, J.J. Spivey, Clean liquid fuels from direct coal liquefaction: chemistry, catalysis technological status and challenges. Energy Environ. Sci. 4, 311–345 (2011)CrossRefGoogle Scholar
  25. 25.
    C.E. Snape, Similarities and differences of coal reactivity in liquefaction and pyrolysis. Fuel 70, 285–287 (1991)CrossRefGoogle Scholar
  26. 26.
    J.R. Gibbins, G.M. Kimber, A.G. Gaines, R. Kandiyoti, Comparison of primary conversions from a flowing-solvent and a mini-bomb reactor: the effect of extended residence times of products in the reaction zone. Fuel 70, 380–385 (1991)CrossRefGoogle Scholar
  27. 27.
    J.R. Gibbins, R. Kandiyoti, Liquefaction of coal in a flowing-solvent reactor. Fuel 70, 909–915 (1991)CrossRefGoogle Scholar
  28. 28.
    R.L. Braun, A.K. Burnham, Analysis of chemical reaction kinetics using a distribution of activation energies and simpler models. Energy Fuels 1, 153–161 (1987)CrossRefGoogle Scholar
  29. 29.
    H.H. Voge, G.M. Good, Thermal cracking of higher paraffins. J. Amer. Chem. Soc. 71, 594–597 (1949)CrossRefGoogle Scholar
  30. 30.
    P.E. Savage, M.T. Klein, Asphaltene reaction pathways. 4. Pyrolysis of tricyclohexane and 2-ethyltetralin. Ind. Eng. Chem. Res. 276, 1348–1356 (1987)Google Scholar
  31. 31.
    A.K. Burnham, R.H. Sanborn, H.R. Gregg, Thermal dealkylation of docecylbenzene and dodecylclyclohexane. Org. Geochem. 28, 755–758 (1998)CrossRefGoogle Scholar
  32. 32.
    F. Behar, F. Lorant, L. Mazeas, Elaboration of a new compositional kinetic schema for oil cracking. Org. Geochem. 39, 764–782 (2008)CrossRefGoogle Scholar
  33. 33.
    J.G. McNab, P.V. Smith, R.L. Betts, The evolution of petroleum. Ind. Eng. Chem. 44, 2556–2563 (1952)CrossRefGoogle Scholar
  34. 34.
    J.H. Henderson, L. Weber, Physical upgrading of heavy crude oils by the application of heat. J. Can. Petr. Tech. 206–212 (1965)Google Scholar
  35. 35.
    P. Ungerer, F. Behar, M. Villalba, O.R. Heum, A. Audibert, Kinetic modelling of oil cracking. Org. Geochem. 13, 857–868 (1988)CrossRefGoogle Scholar
  36. 36.
    J.H. Levy, R.G. Mallon, G.C. Wall, Vapour phase cracking and coking of three shale oils: kinetics in the presence and absence of shale ash. Fuel 66, 358–364 (1987)CrossRefGoogle Scholar
  37. 37.
    K.J. Jackson, A.K. Burnham, R.L. Braun, K.G. Knauss, Temperature and pressure dependence of n-hexadecane cracking. Org. Geochem. 23, 941–953 (1995)CrossRefGoogle Scholar
  38. 38.
    Y.V. Kissin, Catagenesis and composition of petroleum: origin of n-alkanes and isoalkanes in petroleum crudes. Geochim. Cosmochim. Acta 51, 2445–2457 (1987)CrossRefGoogle Scholar
  39. 39.
    B.M. Fabuss, J.O. Smith, C.N. Satterfield, in Advances in Petroleum Chemistry and Refining, ed. by J.J. McKetta. Thermal cracking of pure saturated hydrocarbons,(Interscience, 1964), pp. 157–201Google Scholar
  40. 40.
    F. Doue, G.J. Guiochon, Theoretical and experimental study of the kinetics of thermal decomposition of n-hexadecane, the mechanism, and the composition of the mixture of products obtained. J Chim. Phys. 65, 395–409 (1968)Google Scholar
  41. 41.
    F. Dominé, High pressure pyrolysis of n-hexane, 2,4-dimethylpentane and 1-phenylbutane. Org. Geochem. 17, 619–634 (1991)CrossRefGoogle Scholar
  42. 42.
    R.G. Mallinson, R.L. Braun, C.K. Westbrook, A.K. Burnham, Detailed chemical kinetics study of the role of pressure in butane cracking. Ind. Eng. Chem. Res. 31, 37–45 (1992)CrossRefGoogle Scholar
  43. 43.
    A.K. Burnham, H.R. Gregg, R.L. Braun, Unraveling the kinetics of petroleum destruction by using 1,2-13C isotopically labeled dopants. Energy Fuels 9, 190–191 (1995)CrossRefGoogle Scholar
  44. 44.
    A.K. Burnham, H.R. Gregg, R.L. Ward, K.G. Knauss, S.A. Copenhaver, J.G. Reynolds, R. Sanborn, Decomposition kinetics and mechanism of n-hexadecane-1,2-13C2 and doce-1-ene-1,2-13C2 doped in petroleum and n-hexadecane. Geochim. Cosmochim. Acta 61, 3725–3737 (1997)CrossRefGoogle Scholar
  45. 45.
    E.M. Suuberg, J. Sherman, W.D. Lilly, Product evolution during rapid pyrolysis of green river formation oil shale. Fuel 66, 1176–1184 (1987)CrossRefGoogle Scholar
  46. 46.
    A.K. Burnham, M.F. Singleton, High pressure pyrolysis of green river oil shale, in Geochemistry and Chemistry of Oil Shales, ACS Symposium Series 230, American Chemical Society, 1983, 335–352, ed. by F.P. Miknis, J.F. McKayGoogle Scholar
  47. 47.
    T.-V. Le Doan, N.W. Bostrom, A.K. Burnham, R.L. Kleinberg, A. Pomerantz, P. Allix, Green river oil shale pyrolysis: semi-open conditions. Energy Fuels 27, 6447–6459 (2013)CrossRefGoogle Scholar
  48. 48.
    A.K. Burnham, J.M. McConaghy, Semi-open pyrolysis of oil shale from the Garden gulch member of the green river formation, Energy Fuels 28, 7426–7439 (2014). Correction: doi: 10.1021/acs.energyfuels.5b02010
  49. 49.
    R.L. Braun, A.K. Burnham, Mathematical model of oil generation, degradation, and expulsion. Energy Fuels 4, 132–146 (1990)CrossRefGoogle Scholar
  50. 50.
    S.A Weil, Oil shale hydroretorting laboratory studies at IGT, in Synthetic Fuels from Oil Shale, Symposium Papers, Atlanta GA, Dec. 1979, (Institute of Gas Technology, Chicago, 1980), pp. 353–376Google Scholar
  51. 51.
    S.A. Weil, D.M .Rue, Laboratory studies on hydroretorting Eastern oil shales, in Synthetic Fuels from Oil Shale II, Symposium Papers, Nashville TN, Institute of Gas Technology, Chicago, 1982, 217-227 Oct. 1981Google Scholar
  52. 52.
    F. Hershkowitz, W.N. Olmstead, R.P. Rhodes, K.D. Rose, Molecular mechanism of oil shale pyrolysis in nitrogen and hydrogen atmospheres, in Geochemistry and Chemistry of Oil Shales, ACS Symp. Ser. 230, American Chemical Society, 1983, ed. by F.P. Miknis, J.F. McKay, pp. 301–316Google Scholar
  53. 53.
    A.K. Burnham, J.A. Happe, On the mechanism of kerogen pyrolysis. Fuel 63, 1353–1356 (1984)CrossRefGoogle Scholar
  54. 54.
    D.M. Rue, Correlations describing the pressurized fluidized-bed hydroretorting carbon conversions of six eastern oil shales. Fuel 71, 1443–1446 (1992)CrossRefGoogle Scholar
  55. 55.
    R.C. Ryan, T.D. Fowler, G.L. Beer, V. Nair, Shell’s in situ conversion process—from laboratory to field pilots, in Oil Shale: a Solution to the Liquid Fuel Dilemma, ACS Symp. Ser. 1032, American Chemical Society, 2010, ed. by O.I. Ogunsola, A.M. Hartstein, O. Ogunsola, pp. 161–183Google Scholar
  56. 56.
    Y. Feng, T.V. Le Doan, A.E. Pomerantz, The chemical composition of bitumen in pyrolyzed green river oil shale: characterization by 13C NMR spectroscopy. Energy Fuels 27, 7314–7323 (2013)CrossRefGoogle Scholar
  57. 57.
    P.R. Craddock, T.V. Le Doan, K. Bake, M. Polyakov, A.M. Charsky, Evolution of kerogen and bitumen during thermal maturation via semi-open pyrolysis investigated by infrared spectroscopy. Energy Fuels 29, 2197–2210 (2015)CrossRefGoogle Scholar
  58. 58.
    J.J. Sweeney, A.K. Burnham, Evaluation of a simple model of vitrinite reflectance based on chemical kinetics. AAPG Bull. 74, 1559–1570 (1990)Google Scholar
  59. 59.
    A.K. Burnham, J.J. Sweeney, A chemical kinetic model of vitrinite maturation and reflectance. Geochim. Cosmochim. Acta 53, 2649–657 (1989)Google Scholar
  60. 60.
    A.K. Burnham, A.E. Pomerantz, F. Gelin, Oil, bitumen, and other confusing concepts: what do laboratory experiments really tell us?. AAPG Bull. submitted (2016)Google Scholar
  61. 61.
    G.L. Baughman (ed.), Synthetic Fuels Handbook, 2nd edn. (Cameron Eng, Denver, 1978), pp. 59–62Google Scholar
  62. 62.
    M.F. Singleton, G.J. Koskinas, A.K. Burnham, J.H. Raley, Assay Products from Green River Oil Shale, Lawrence Livermore National Laboratory UCRL-53273 Rev. 1, 1986Google Scholar
  63. 63.
    D.A. Netzel, F.P. Miknis, Hydrocarbon type analysis of eastern and western shale oils produced by the IGT Hytort and Fischer Assay processes, in Synthetic Fuels from Oil Shale II, Symposium Papers, Nashville TN, Oct. 1981, (Institute of Gas Technology, Chicago, 1982), pp. 229–250Google Scholar
  64. 64.
    P.A. Lynch, J.C. Janka, F.S. Lau, H.L. Felkirchner, H.A. Dirksen, The hydroretorting assay—a new technique for oil shale assessment. Prepr. ACS Div. Petr. Chem. 29(1), 71–75 (1989)Google Scholar
  65. 65.
    S.D. Carter, M. Citiroglu, J. Gallacher, C.E. Snape, S. Mitchell, C.J. Lafferty, Secondary coking and cracking of shale oil vapours from pyrolysis or hydropyrolysis of a Kentucky Cleveland member oil shale in a two-stage reactor. Fuel 73, 1455–1458 (1994)CrossRefGoogle Scholar

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© Springer International Publishing AG 2017

Authors and Affiliations

  1. 1.LivermoreUSA

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