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A Size-Dependent Thermodynamic Model for Coke Crystallites: The Carbon-Sulfur System Up to 2500 K (2227 °C)

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Abstract

A model is presented for the development of the thermodynamic functions of enthalpy, entropy, and Gibbs energy for the elements carbon and sulfur in coke crystallites. The crystallites of various degrees of graphitization may be described by crystallite length L a and crystallite height L c. This carbon/sulfur model has been developed using concepts similar to those in the carbon/hydrogen model for coke crystallites. The major model parameters are derived from reported thermodynamic properties. Approximately 75 pct of the model parameters for the carbon/hydrogen and carbon/sulfur system are parameters common to both systems. The resulting crystallite size (L a) constrained in the carbon/sulfur phase diagram, computed by a Gibbs energy minimization technique, is presented for 1 atm and temperatures between 1500 K and 2500 K (1227 °C and 2227 °C). A very good agreement is obtained between the predicted thermal desulfurization of petroleum cokes and critically assessed experimental data. The removal of sulfur from coke crystallites is predicted to occur mostly between 1600 K and 1850 K (1327 °C and 1577 °C) at 1 atm, depending on the L a value. The precision in the predictive calculations and the transferability of the model parameters are two aspects that tend to support the usefulness and the theoretical basis of the entire approach.

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Acknowledgments

We would like to thank Dr. James M. Sangster for his participation in the review of this paper. This project was supported by the Natural Sciences and Engineering Research Council of Canada, Alcoa, Hydro Aluminum, and Rio Tinto Alcan. Mr. Ouzilleau also acknowledges Rio Tinto Alcan for a scholarship.

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Authors and Affiliations

  1. Centre for Research in Computational Thermochemistry (CRCT), Department of Chemical Engineering, École Polytechnique, C.P. 6079, Succursale “Downtown”, Montreal, QC, H3C 3A7, Canada

    Philippe Ouzilleau (Ph.D. Candidate), Aïmen E. Gheribi (Research Associate) & Patrice Chartrand (Professor)

  2. Åbo Akademi Process Chemistry Centre Inorganic Chemistry, Abo Akademi University, 20500, Turku Abo, Finland

    Daniel K. Lindberg (Senior Researcher)

Authors
  1. Philippe Ouzilleau
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  2. Aïmen E. Gheribi
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  3. Daniel K. Lindberg
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  4. Patrice Chartrand
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Correspondence to Patrice Chartrand.

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Manuscript submitted April 8, 2015.

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Ouzilleau, P., Gheribi, A.E., Lindberg, D.K. et al. A Size-Dependent Thermodynamic Model for Coke Crystallites: The Carbon-Sulfur System Up to 2500 K (2227 °C). Metall Mater Trans B 47, 1817–1831 (2016). https://doi.org/10.1007/s11663-016-0643-8

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