Energetic and Exergetic Performance Comparisons of Various Flow Sheet Options of Magnesium-Chlorine Cycle

  • Hasan OzcanEmail author
  • Ibrahim Dincer
Part of the Green Energy and Technology book series (GREEN)


During the past decade thermochemical and/or hybrid cycles using essentially heat (without/with some electricity) are preferred over conventional electrolysis where the electricity is the main energy input. Therefore, such cycles help significantly reduce the electrical work consumption by adapting some consecutive chemical reactions which utilize thermal energy at medium to low temperatures that can match with renewable and existing nuclear energy sources. The ideal magnesium-chlorine cycle consists of three steps, namely hydrolysis of MgCl2, chlorination of MgO, and electrolysis of HCl. In this particular study, we develop two newly proposed configurations to compare with the ideal version of this cycle. The first configuration uses an intermediate step through the hydrolysis reaction while a fourth step is introduced in the second configuration where HCl production is accomplished in dry form. Thermodynamic comparisons are carried out using energy and exergy analysis, and the four-step configuration practically shows the highest performance and can compete with the conventional splitting of water by electrolysis. In summary, the present options provide potential solutions for sustainable hydrogen production.


Mg-Cl cycle Hybrid thermochemical water splitting Anhydrous HCl Energy Exergy 


  1. Bartling, J., Winnick, J.: Chlorine recovery from anhydrous hydrogen chloride in a molten salt electrolyte membrane cell. J. Electrochem. Soc. 150, D99–D107 (2003)CrossRefGoogle Scholar
  2. Carmo, M., Fritz, D.L., Mergel, J., Stolten, D.: A comprehensive review on PEM water electrolysis. Int. J. Hydrog. Energy. 38, 4901–4934 (2013)CrossRefGoogle Scholar
  3. Dincer, I., Rosen, M.A.: Exergy: Energy, Environment and Sustainable Development. Newnes, London (2012)Google Scholar
  4. Dincer, I., Zamfirescu, C.: Sustainable hydrogen production options and role of AIHE. Int. J. Hydrog. Energy. 37, 16266–16286 (2012)CrossRefGoogle Scholar
  5. Eames, D.J., Newman, J.: Electrochemical conversion of anhydrous HCl to Cl2 using a solid-polymer-electrolyte electrolysis cell. J. Electrochem. Soc. 142, 3619–3625 (1995)CrossRefGoogle Scholar
  6. Gooding, C.H.: Analysis of alternative flow sheets for the hybrid chlorine cycle. Int. J. Hydrog. Energy. 34, 4168–4178 (2009)CrossRefGoogle Scholar
  7. Hesson, R.N.: Kinetics of the chlorination of magnesium oxide, No. IS-T-823. Ames Lab., IA (USA) (1979)Google Scholar
  8. Kashani-Nejad, S., Ng, K.-W., Harris, R.: Preparation of MgOHCl by controlled dehydration of MgCl2· 6H2 O. Metall. Mater. Trans. B. 35, 405–406 (2004)CrossRefGoogle Scholar
  9. Kashani-Nejad, S., Ng, K.-W., Harris, R.: MgOHCl thermal decomposition kinetics. Metall. Mater. Trans. B. 36, 153–157 (2005)CrossRefGoogle Scholar
  10. Kashani-Nejad, S., Ng, K.W., Harris, R.: Chlorination of MgOHCl with HCl gas. Miner. Process. Ext. Metall. 115, 121–122 (2006)CrossRefGoogle Scholar
  11. Kelley, K.K.: Energy requirements and equilibria in the dehydration, hydrolysis, and decomposition of Magnesium-Chloride. U.S. Department of Interior, US Govt. Print. Off, Technical Paper (1945)Google Scholar
  12. Kipouros, G.J., Sadoway, D.R.: A thermochemical analysis of the production of anhydrous MgCl 2. J. Light. Met. 1, 111–117 (2001)CrossRefGoogle Scholar
  13. Lewis, M.A., Masin, J.G., O’Hare, P.A.: Evaluation of alternative thermochemical cycles. Part I: the methodology. Int. J. Hydrog. Energy. 34, 4115–4124 (2009)CrossRefGoogle Scholar
  14. Motupally, S., Becker, A.J., Weidner, J.W.: Water transport in polymer electrolyte membrane electrolyzers used to recycle anhydrous HCl I. Characterization of diffusion and electro-osmotic drag. J. Electrochem. Soc. 149, D63–D71 (2002)CrossRefGoogle Scholar
  15. Naterer, G.F., Dincer, I., Zamfirescu, C.: Hydrogen Production from Nuclear Energy. Springer, London (2013)CrossRefGoogle Scholar
  16. Ozcan, H., Dincer, I.: Performance investigation of magnesium–chloride hybrid thermochemical cycle for hydrogen production. Int. J. Hydrog. Energy. 39, 76–85 (2014a)CrossRefGoogle Scholar
  17. Ozcan, H., Dincer, I.: Energy and exergy analyses of a solar driven Mg–Cl hybrid thermochemical cycle for co-production of power and hydrogen. Int. J. Hydrogen Energy. 39, 15330–15341 (2014b)CrossRefGoogle Scholar
  18. Ozcan, H., Dincer, I.: Modeling of a new four-step magnesium–chlorine cycle with dry HCl capture for more efficient hydrogen production. Int. J. Hydrogen Energy. 41, 7792–7801 (2016a)CrossRefGoogle Scholar
  19. Ozcan, H., Dincer, I.: Comparative performance assessment of three configurations of magnesium–chlorine cycle. Int. J. Hydrogen Energy. 41, 845–856 (2016b)CrossRefGoogle Scholar
  20. Simpson, M.F., Hermann, S.D., Boyle, B.D.: A hybrid thermochemical electrolytic process for hydrogen production based on the reverse Deacon reaction. Int. J. Hydrog. Energy. 31, 1241–1246 (2006)CrossRefGoogle Scholar
  21. Sivasubramanian, P., Ramasamy, R.P., Freire, F.J., Holland, C.E., Weidner, J.W.: Electrochemical hydrogen production from thermochemical cycles using a proton exchange membrane electrolyzer. Int. J. Hydrog. Energy. 32, 463–468 (2007)CrossRefGoogle Scholar
  22. Veziroglu, T.N., Barbir, F.: Hydrogen: the wonder fuel. Int. J. Hydrog. Energy. 17, 391–404 (1992)CrossRefGoogle Scholar
  23. Yan, X.L., Hino, R.: Nuclear Hydrogen Production Handbook, pp. 50–54. CRC Press, Boca Raton (2011)CrossRefGoogle Scholar

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© Springer International Publishing AG, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Faculty of Engineering and Applied Science, Department of Mechanical EngineeringUniversity of Ontario Institute of TechnologyOshawaCanada

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