Journal of Mechanical Science and Technology

, Volume 33, Issue 11, pp 5561–5569 | Cite as

Catalytic hydrogenation and dehydrogenation performance of 9-ethylcarbazole as a liquid organic hydrogen carrier

  • Ahsan Ali
  • Udaya Kumar G
  • Hee Joon LeeEmail author


The hydrogenation characteristics of 9-ethylcarbazole (9-ECZ) over Raney-Ni catalyst within the pressure range 0.2–0.8 MPa was investigated in this work. Initially, hydrogenation experiments were performed over various catalysts which revealed that 5 wt.% Ru/Al2O3 was the most active catalyst, whereas, Raney-Ni being least expensive was chosen for this study. Ten grams of 9-ECZ and 1 g of Raney-Ni were added to the stirrer type reactor, the effect of various parameters such as temperature, pressure, catalyst dosage, and stirring speed were examined. The results indicated that the optimal reaction temperature was 160 °C at a maximal pressure (0.8 MPa), stirring speed (800 rpm). Furthermore, 2 g of 9-ECZ was used with Raney-Ni dosages of 0.2 and 1.0 g and the corresponding hydrogen uptake was 5.16 wt.% and 5.81 wt.%, respectively. Lastly, three cyclic experiments were conducted to investigate the reversibility of the hydrogenation and dehydrogenation of 9-ECZ at 180 °C.


Dehydrogenation Hydrogenation Liquid organic hydrogen carrier Reversibility 9-ethylcarbazole 


a, b

Arbitrary constants


Change in the mass of hydrogen gas


Mass of solution


No of moles of hydrogen gas


Initial concentration of the gas


Final concentration of the gas


Pressure of hydrogen gas


Ideal gas constant


Temperature of the reactor


Volume of hydrogen gas


Weight percent of stored hydrogen gas


Volume of the bottle


Output value of ultrasonic level transmitter


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This work was supported by the National Research Foundation of Korea (NRF) grant funded by the Korea government (MSIT) (NRF-2018R1A2B6006160). This work was supported by Global Scholarship Program for Foreign Graduate Students at Kookmin University in Korea.


  1. [1]
    N. Kariya, A. Fukuoka, T. Utagawa and M. Sakuramoto, Efficient hydrogen production using cyclohexane and decalin by pulse-spray mode reactor with Pt catalysts, Appl. Catal. A: Gen., 247 (2003) 247–259.Google Scholar
  2. [2]
    R. B. Biniwale, S. Rayalu, S. Devotta and M. Ichikawa, Chemical hydrides: A solution to high capacity hydrogen storage and supply, Int. J. Hydrogen Energy, 33 (1) (2008) 360–365.Google Scholar
  3. [3]
    J. Lee, J. H. Han, J. H. Moon, C. H. Jeong, M. Kim, J. Y. Kim and S. H. Lee, Characteristics of heat transfer and chemical reaction of methane-steam reforming in a porous catalytic medium, J. Mech. Sci. Technol., 30 (1) (2016) 473–481.Google Scholar
  4. [4]
    T. Jo, B. Koo, Y. Lee, H. So and D. Lee, Numerical and experimental study on the thermal characteristics of a steam reformer, J. Mech. Sci. Technol., 32 (2) (2018) 679–687.Google Scholar
  5. [5]
    J. Zheng, X. Liu, P. Xu, P. Liu, Y. Zhao and J. Yang, Development of high pressure gaseous hydrogen storage technologies, Int. J. Hydrogen Energy, 37 (1) (2011) 1048–1057.Google Scholar
  6. [6]
    W. Peschka and C. Carpetis, Cryogenic hydrogen storage and refueling for automobiles, Int. J. Hydrogen Energy, 5 (1980) 619–625.Google Scholar
  7. [7]
    A. C. Dillon, K. M. Jones, T. A. Bekkedahl, C. H. Kiang, D. S. Bethune and M. J. Heben, Storage of hydrogen in single-walled carbon nanotubes, Nature, 386 (6623) (1997) 377–379.Google Scholar
  8. [8]
    H. Cheng, Q. Yang and C. Liu, Hydrogen storage in carbon nanotubes, Carbon, 39 (2001) 1447–1454.Google Scholar
  9. [9]
    J. Y. Hwang, S. H. Lee, K. S. Sim and J. W. Kim, Synthesis and hydrogen storage of carbon nanofibers, Synthetic Metals, 126 (3) (2002) 81–85.Google Scholar
  10. [10]
    D.L. Cummings and G. J. Powers, The storage of hydrogen as metal hydrides, Ind. Eng. Chem. Process Des. Develop, 13 (2) (1974) 182–192.Google Scholar
  11. [11]
    M. Felderhoff, F. Schu and B. Bogdanovic, Light metal hydrides and complex hydrides for hydrogen storage, Chem. Commun. (2004) 2249–2258.Google Scholar
  12. [12]
    E. Rönnebro, Development of group II borohydrides as hydrogen storage materials, Current Opinion in Solid State and Materials Sci., 15 (2011) 44–51.Google Scholar
  13. [13]
    M. L. Schmitt, J. E. Shelby and M. M. Hall, Preparation of hollow glass microspheres from sol - gel derived glass for application in hydrogen gas storage, J. Non-Crystalline Solids, 352 (2006) 626–631.Google Scholar
  14. [14]
    A. Boudjahem, W. Bouderbala and M. Bettahar, Benzene hydrogenation over Ni - Cu / SiO2 catalysts prepared by aqueous hydrazine reduction, Fuel Process. Technol., 92 (3) (2011) 500–506.Google Scholar
  15. [15]
    S. Nassreddine, L. Massin, M. Aouine, C. Geantet and L. Piccolo, Thiotolerant Ir / SiO2 - Al2O3 bifunctional catalysts: Effect of metal - acid site balance on tetralin hydroconversion, J. Catal., 278 (2) (2011) 253–265.Google Scholar
  16. [16]
    J. V. Pande, A. Shukla and R. B. Biniwale, Catalytic dehydrogenation of cyclohexane over Ag-M / ACC catalysts fo r hydrogen supply, Int. J. Hydrogen Energy, 37 (8) (2012) 6756–6763.Google Scholar
  17. [17]
    W. Wang, H. Liu, T. Wu, P. Zhang, G. Ding and S. Liang, Chemical ru catalyst supported on bentonite for partial hydrogenation of benzene to cyclohexene, J. Mol. Catal. A, Chem., 355 (2012) 174–179.Google Scholar
  18. [18]
    M. Wojciechowska, Iridium supported on MgF2 - MgO as catalyst for toluene hydrogenation, Catal. Commun., 18 (2012) 1–4.Google Scholar
  19. [19]
    D. Koutsonikolas, S. Kaldis, V. T. Zaspalis and G. P. Sakellaropoulos, Potential application of a microporous silica membrane reactor for cyclohexane dehydrogenation, Int. J. Hydrogen Energy, 37 (21) (2012) 16302–16307.Google Scholar
  20. [20]
    L. Zhang, G. Xu, Y. An, C. Chen and Q. Wang, Dehydrogenation of methyl-cyclohexane under multiphase reaction conditions, Int. J. Hydrogen Energy, 31 (2006) 2250–2255.Google Scholar
  21. [21]
    D. Mori and K. Hirose, Recent challenges of hydrogen storage technologies for fuel cell vehicles, Int. J. Hydrogen Energy, 34 (10) (2009) 4569–4574.Google Scholar
  22. [22]
    Z. Jiang, Q. Pan, J. Xu and T. Fang, Current situation and prospect of hydrogen storage technology with new organic liquid, Int. J. Hydrogen Energy, 39 (30) (2014) 1–10.Google Scholar
  23. [23]
    K. M. Eblagon, D. Rentsch, O. Friedrichs, A. Remhof, A. Zuettel, A. J. Ramirez-Cuesta and S. C. Tsang, Hydrogenation of 9-ethylcarbazole as a prototype of a liquid hydrogen carrier, Int. J. Hydrogen Energy, 35 (20) (2010) 11609–11621.Google Scholar
  24. [24]
    C. Wan, Y. An, G. Xu and W. Kong, Study of catalytic hydrogenation of N-ethylcarbazole over ruthenium catalyst, Int. J. Hydrogen Energy, 37 (17) (2012) 13092–13096.Google Scholar
  25. [25]
    C. Wan, Y. An, F. Chen, D. Cheng, F. Wu and G. Xu, Kinetics of N-ethylcarbazole hydrogenation over a supported ru catalyst for hydrogen storage, Int. J. Hydrogen Energy, 38 (17) (2013) 7065–7069.Google Scholar
  26. [26]
    X. Ye, Y. An and G. Xu, Kinetics of 9-ethylcarbazole hydrogenation over Raney-Ni catalyst for hydrogen storage, J. Alloys Compd., 509 (1) (2011) 152–156.Google Scholar
  27. [27]
    O. Z. Tajrishi, M. Taghizadeh and A. D. Kiadehi, Methanol steam reforming in a microchannel reactor by Zn-, Ce- and Zr-modified mesoporous Cu/SBA-15 nanocatalyst, Int. J. Hydrogen Energy, 43 (31) (2018) 14103–14120.Google Scholar
  28. [28]
    M. Pan, Q. Wu, L. Jiang and D. Zeng, Effect of microchannel structure on the reaction performance of methanol steam reforming, Appl. Energy, 154 (2015) 416–427.Google Scholar
  29. [29]
    W. Cai, F. Wang, A. van Veen, C. Descorme, Y. Schuurman, W. Shen and C. Mirodatos, Hydrogen production from ethanol steam reforming in a micro-channel reactor, Int. J. Hydrogen Energy, 35 (3) (2010) 1152–1159.Google Scholar
  30. [30]
    M. Yang, Y. Dong, S. Fei, H. Ke and H. Cheng, A comparative study of catalytic dehydrogenation of perhydro-N-ethylcarbazole over noble metal catalysts, Int. J. Hydrogen Energy, 39 (33) (2014) 18976–18983.Google Scholar
  31. [31]
    B. Wang, T. Yan, T. Chang, J. Wei, Q. Zhou, S. Yang and T. Fang, Palladium supported on reduced graphene oxide as a highperformance catalyst for the dehydrogenation of dodecahydro-N - ethylcarbazole, Carbon N. Y., 122 (2017) 9–18.Google Scholar
  32. [32]
    Z. Jiang, X. Gong, B. Wang, Z. Wu and T. Fang, A experimental study on the dehydrogenation performance of dodecahydro-N-ethylcarbazole on M/TiO2 catalysts, Int. J. Hydrogen Energy, 44 (5) (2019) 2951–2959.Google Scholar
  33. [33]
    B. Wang, T. yan Chang, Z. Jiang, J. jia Wei, Y. hai Zhang, S. Yang and T. Fang, Catalytic dehydrogenation study of dodecahydro-N-ethylcarbazole by noble metal supported on reduced graphene oxide, Int. J. Hydrogen Energy, 43 (15) (2018) 7317–7325.Google Scholar
  34. [34]
    F. Sotoodeh, L. Zhao and K. J. Smith, Kinetics of H2 recovery from dodecahydro-N-ethylcarbazole over a supported Pd catalyst, Appl. Catal. A Gen., 362 (1–2) (2009) 155–162.Google Scholar
  35. [35]
    J. Manna, B. Roy, M. Vashistha and P. Sharma, Effect of Co+2/BH4- ratio in the synthesis of Co-B catalysts on sodium borohydride hydrolysis, Int. J. Hydrogen Energy, 39 (1) (2014) 406–413.Google Scholar
  36. [36]
    Y. Shang, R. Chen and G. Jiang, Kinetic study of NaBH4 hydrolysis over carbon-supported ruthenium, Int. J. Hydrogen Energy, 33 (22) (2008) 6719–6726.Google Scholar
  37. [37]
    M. H. Loghmani, A. F. Shojaei and M. Khakzad, Hydrogen generation as a clean energy through hydrolysis of sodium borohydride over Cu-Fe-B nano powders: Effect of polymers and surfactants, Energy, 126 (2017) 830–840.Google Scholar
  38. [38]
    D. Kılınç, Ö. Şahin and C. Saka, Investigation on salisylaldimine-Ni complex catalyst as an alternative to increasing the performance of catalytic hydrolysis of sodium borohydride, Int. J. Hydrogen Energy, 42 (32) (2017) 20625–20637.Google Scholar
  39. [39]
    Ö Şahin, D. Kılınç and C. Saka, Hydrogen generation from hydrolysis of sodium borohydride with a novel palladium metal complex catalyst, J. Energy Inst., 89 (2) (2016) 182–189.Google Scholar
  40. [40]
    M. Yang, C. Han, G. Ni, J. Wu and H. Cheng, Temperature controlled three-stage catalytic dehydrogenation and cycle performance of perhydro-9-ethylcarbazole, Int. J. Hydrogen Energy, 37 (17) (2012) 12839–12845.Google Scholar
  41. [41]
    A.Y. Cengel and A. M. Boles, Thermodynamic an Engineering Approach, 5th Ed., (2004) Ch. 3, 138–142.Google Scholar
  42. [42]
    A.D. Kiadehi and M. Taghizadeh, Evaluation of a microchannel reactor for steam reforming of ethylene glycol: A comparative study of catalytic activity of Pt or/and Ni supported Γ-alumina catalysts, Int. J. Hydrogen Energy, 43 (10) (2018) 4826–4838.Google Scholar
  43. [43]
    K. Marcin, W. Waldemar, B. Robert and G. Andrzej, The influence of the hydrogen pressure on kinetics of the canola oil hydrogenation on industrial nickel catalyst, Catalysts, 6 (55) (2016) 1–14.Google Scholar
  44. [44]
    C.L. Aardahl and S. D. Rassat, Overview of systems considerations for on-board chemical hydrogen storage, Int. J. Hydrogen Energy, 34 (16) (2009) 6676–6683.Google Scholar
  45. [45]
    S.G. Chalk and J. F. Miller, Key challenges and recent progress in batteries, fuel cells, and hydrogen storage for clean energy systems, J. Power Sources, 159 (1 SPEC. ISS.) (2006) 73–80.Google Scholar
  46. [46]
    Y. Dong, M. Yang, P. Mei, C. Li and L. Li, Dehydrogenation kinetics study of perhydro-N-ethylcarbazole over a supported Pd catalyst for hydrogen storage application, Int. J. Hydrogen Energy, 41 (20) (2016) 8498–8505.Google Scholar
  47. [47]
    F. Sotoodeh and K. J. Smith, Kinetics of hydrogen uptake and release from heteroaromatic compounds for hydrogen storage, Ind. Eng. Chem. Res., 49 (3) (2010) 1018–1026.Google Scholar
  48. [48]
    F. Sotoodeh and K. J. Smith, Structure sensitivity of dodecahydro-N-ethylcarbazole dehydrogenation over Pd catalysts, J. Catal., 279 (1) (2011) 36–47.Google Scholar

Copyright information

© KSME & Springer 2019

Authors and Affiliations

  1. 1.School of Mechanical EngineeringKookmin UniversitySeoulKorea

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