Thermodynamic analysis of steam reforming of glycerol for hydrogen production at atmospheric pressure

Abstract

Thermodynamic chemical equilibrium analysis of steam reforming of glycerol (SRG) for selective hydrogen production was performed based on the Gibbs free energy minimisation method. The ideal SRG reaction (C₃H₈O₃+3H₂O→3CO₂+7H₂) and a comprehensive set of side reactions during SRG are considered for the formation of a wide range of products. Specifically, this work focused on the analysis of formation of H_2, CO₂, CO and CH₄ in the gas phase and determination of the carbon free region in SRG under the conditions at atmospheric pressure, 600 K–1100 K and 1.013 × 10⁵–1.013 × 10⁶ Pa with the steam-to-glycerol feed ratios (SGFR) of 1:5–10. The reaction conditions which favoured SRG for H₂ production with minimum coke formation were identifies as: atmospheric pressure, temperatures of 900 K–1050 K and SGFR of 10:1. The influence of using the inert carrier gas (i.e., N₂) in SRG was studied as well at atmospheric pressure. Although the presence of N₂ in the stream decreased the partial pressure of reactants, it was beneficial to improve the equilibrium yield of H₂. Under both conditions of SRG (with/without inert gas), the CH₄ production is minimised, and carbon formation was thermodynamically unfavoured at steam rich conditions of SGFR>5:1.

Graphical abstract

Keywords

steam reforming of glycerol / H₂ / N₂ / carbon deposition / thermodynamic analysis / Gibbs free energy minimisation

References

[1] Papageridis K N, Siakavelas G, Charisiou N D, Avraam D G, Tzounis L, Kousi K, Goula M A. Comparative study of Ni, Co, Cu supported on g-alumina catalysts for hydrogen production via the glycerol steam reforming reaction. Fuel Processing Technology, 2016, 152: 156–175

[2] Zhou C H, Zhao H, Tong D S, Wu L M, Yu W H. Recent advances in catalytic conversion of glycerol. Catalysis Reviews, 2013, 55(4): 369–453

[3] Buffoni I N, Pompeo F, Santori G F, Nichio N N. Nickel catalysts applied in steam reforming of glycerol for hydrogen production. Catalysis Communications, 2009, 10(13): 1656–1660

[4] Wang W. Thermodynamic analysis of glycerol partial oxidation for hydrogen production. Fuel Processing Technology, 2010, 91(11): 1401–1408

[5] Yang G, Yu H, Peng F, Wang H, Yang J, Xie D. Thermodynamic analysis of hydrogen generation via oxidative steam reforming of glycerol. Renewable Energy, 2011, 36(8): 2120–2127

[6] Avasthi K S, Reddy R N, Patel S. Challenges in the production of hydrogen from glycerol—a biodiesel byproduct via steam reforming process. Procedia Engineering, 2013, 51: 423–429

[7] Schwengber C A, Alves H J, Schaffner R A, da Silva F A, Sequinel R, Bach V R, Ferracin R J. Overview of glycerol reforming for hydrogen production. Renewable & Sustainable Energy Reviews, 2016, 58: 259–266

[8] Dou B, Song Y, Wang C, Chen H, Xu Y. Hydrogen production from catalytic steam reforming of biodiesel byproduct glycerol: issues and challenges. Renewable & Sustainable Energy Reviews, 2014, 30: 950–960

[9] Bagnato G, Iulianelli A, Sanna A, Basile A. Glycerol production and transformation: a critical review with particular emphasis on glycerol reforming reaction for producing hydrogen in conventional and membrane reactors. Membranes, 2017, 7(2): 17

[10] Roslan N A, Abidin S Z, Ideris A, Vo D V N. A review on glycerol reforming processes over Ni-based catalyst for hydrogen and syngas productions. International Journal of Hydrogen Energy, 2020, 45(36): 18466–18489

[11] Chen H, Ding Y, Cong N T, Dou B, Dupont V, Ghadiri M, Williams P T. A comparative study on hydrogen production from steam-glycerol reforming: thermodynamics and experimental. Renewable Energy, 2011, 36(2): 779–788

[12] Silva J M, Soria M A, Madeira L M. Thermodynamic analysis of glycerol steam reforming for hydrogen production with in situ hydrogen and carbon dioxide separation. Journal of Power Sources, 2015, 273: 423–430

[13] Lin K H, Lin W H, Hsiao C H, Chang H F, Chang A C C. Hydrogen production in steam reforming of glycerol by conventional and membrane reactors. International Journal of Hydrogen Energy, 2012, 37(18): 13770–13776

[14] Iulianelli A, Seelam P K, Liguori S, Longo T, Keiski R, Calabrò V, Basile A. Hydrogen production for PEM fuel cell by gas phase reforming of glycerol as byproduct of bio-diesel. The use of a Pd-Ag membrane reactor at middle reaction temperature. International Journal of Hydrogen Energy, 2011, 36(6): 3827–3834

[15] Silva J M, Soria M A, Madeira L M. Challenges and strategies for optimization of glycerol steam reforming process. Renewable & Sustainable Energy Reviews, 2015, 42: 1187–1213

[16] Adhikari S, Fernando S D, Haryanto A. Hydrogen production from glycerin by steam reforming over nickel catalysts. Renewable Energy, 2008, 33(5): 1097–1100

[17] Adhikari S, Fernando S, Gwaltney S, Filipto S, Markbricka R, Steele P, Haryanto A. A thermodynamic analysis of hydrogen production by steam reforming of glycerol. International Journal of Hydrogen Energy, 2007, 32(14): 2875–2880

[18] Wang X, Li M, Wang M, Wang H, Li S, Wang S, Ma X. Thermodynamic analysis of glycerol dry reforming for hydrogen and synthesis gas production. Fuel, 2009, 88(11): 2148–2153

[19] Wang H, Wang X, Li M, Li S, Wang S, Ma X. Thermodynamic analysis of hydrogen production from glycerol autothermal reforming. International Journal of Hydrogen Energy, 2009, 34(14): 5683–5690

[20] Li J, Yu H, Yang G, Peng F, Xie D, Wang H, Yang J. Steam reforming of oxygenate fuels for hydrogen production: a thermodynamic study. Energy & Fuels, 2011, 25(6): 2643–2650

[21] Fasolini A, Cespi D, Tabanelli T, Cucciniello R, Cavani F. Hydrogen from renewables: a case study of glycerol reforming. Catalysts, 2019, 9(9): 772

[22] Smith J M, Van Ness H C, Abbott M M. Introduction to Chemical Engineering Thermodynamics. 7th ed. New York: McGraw-Hill, 2005, 450–508

[23] Tahir M, Mulewa W, Amin N A S, Zakaria Z Y. Thermodynamic and experimental analysis on ethanol steam reforming for hydrogen production over Ni-modified TiO₂/MMT nanoclay catalyst. Energy Conversion and Management, 2017, 154: 25–37

[24] ChemCAD process simulator. Version 6.5.6. Houston, TX: Chemstations, Inc., 2012

[25] Nikoo M K, Amin N A S. Thermodynamic analysis of carbon dioxide reforming of methane in view of solid carbon formation. Fuel Processing Technology, 2011, 92(3): 678–691

[26] Cheng C K, Foo S Y, Adesina A A. Thermodynamic analysis of glycerol-steam reforming in the presence of CO₂ or H₂ as carbon gasifying agent. International Journal of Hydrogen Energy, 2012, 37(13): 10101–10110

[27] Charisiou N D, Papageridis K N, Siakavelas G, Tzounis L, Kousi K, Baker M A, Hinder S J, Sebastian V, Polychronopoulou K, Goula M A. Glycerol steam reforming for hydrogen production over nickel supported on alumina, zirconia and silica catalysts. Topics in Catalysis, 2017, 60(15-16): 1226–1250

[28] Charisiou N D, Polychronopoulou K, Asif A, Goula M A. The potential of glycerol and phenol towards H₂ production using steam reforming reaction: a review. Surface and Coatings Technology, 2018, 352: 92–111

[29] Cantelo R C. The thermal decomposition of methane. Journal of Physical Chemistry, 1924, 28(10): 1036–1048

[30] Gallo A, Pirovano C, Ferrini P, Marelli M, Psaro R, Santangelo S, Faggio G, Dal Santo V. Influence of reaction parameters on the activity of ruthenium based catalysts for glycerol steam reforming. Applied Catalysis B: Environmental, 2012, 121-122: 40–49

[31] Sundari R, Vaidya P D. Reaction kinetics of glycerol steam reforming using a Ru/Al₂O₃ catalyst. Energy & Fuels, 2012, 26(7): 4195–4204

Acknowledgements

This project has received funding from European Union’s Horizon 2020 research and innovation programme under grant agreement No. 872102. Ammaru Ismaila thanks the financial support by the Petroleum Technology Development Fund (PTDF) Nigeria for his PhD research at The University of Manchester (File No. PTDF/ED/OSS/PHD/IA/1209/17).

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