PROGRESS ON HYDROGEN PRODUCTION BY STEAM REFORMING OF GLYCEROL

Abstract

Abstract: Glycerol steam reforming represents a pivotal technological pathway for the value-added utilization of glycerol, a by-product of biodiesel production, and for the generation of green hydrogen. The industrial application of this reaction centers on the development of catalysts that exhibit high activity, high selectivity, and superior stability. This paper systematically reviews recent research progress in catalyst design for hydrogen production by glycerol steam reforming, focusing on the three key aspects: active metals, supports, and promoters. It provides an in-depth analysis of the construction of catalyst active sites, metal-support interactions, and the regulatory mechanisms for enhancing resistance to coking and sintering. Finally, it analyzes the theoretical and technical challenges currently facing catalyst design and outlines future development directions.

Key words: glycerol, hydrogen production, steam reforming, catalyst design

References

[1] WANG Z, SUN Y, KONG H, et al. An in-depth review of key technologies and pathways to carbon neutrality: classification and assessment of decarbonization technologies [J]. Carbon Neutrality, 2025, 4(1). [2] LI D, LI Y, LIU X, et al. NiAl2O4 Spinel Supported Pt Catalyst: High Performance and Origin in Aqueous-Phase Reforming of Methanol [J]. ACS Catalysis, 2019, 9(10): 9671-82. [3] GAO K, SAHRAEI O A, ILIUTA M C. Development of residue coal fly ash supported nickel catalyst for H2 production via glycerol steam reforming [J]. Applied Catalysis B: Environmental, 2021, 291. [4] ZHU S, MA S, SONG D, et al. Dependence of the strong metal-support interactions of Ni/TiO2 and the induction period of glycerol steam reforming on the dynamic crystal phase evolution [J]. Chemical Engineering Journal, 2024, 489. [5] USMAN M, GHANEM A S, GARBA M D, et al. Green and blue hydrogen production and purification technologies [J]. International Journal of Hydrogen Energy, 2025, 153: 150176. [6] NIU Y, ZENG X, XIA J, et al. Recent progress of green hydrogen production technology [J]. Frontiers of Chemical Science and Engineering, 2025, 19(10): 93. [7] AIE. The Future of Hydrogen:Seizing today’s opportunities [M]. OECD;OCDE, 2019. [8] HASSANPOURYOUZBAND A, VESHAREH M J, WILKINSON M, et al. In situ hydrogen generation from underground fossil hydrocarbons [J]. Joule, 2025, 9(2): 101809. [9] COLLANA J T M, VENEGAS L C, DEXTRE C A, et al. Analysis of the Main Hydrogen Production Technologies [J]. Sustainability, 2025, 17(18): 8367. [10] LUO G, ZHAO Z T, DING J, et al. Comparative review of carbon emissions from hydrogen production technologies: The hydrogen color characteristic of biomass-based manufacturing [J]. Renewable and Sustainable Energy Reviews, 2025, 217: 115756. [11] KHOO H H, HO E H Z, YAP K S, et al. Life Cycle Assessment of biomass resources for hydrogen production [J]. The Science of the total environment, 2025, 1002: 180587. [12] PUTERI M N, GEW L T, ONG H C, et al. Biomass-to-biohydrogen conversion: Comprehensive analysis of processes, environmental, and economic implications [J]. Biomass and Bioenergy, 2025, 200: 107943. [13] MUSTAPHA S I, ANEKWE I M S, AKPASI S O, et al. Biomass conversion for sustainable hydrogen generation: A comprehensive review [J]. Fuel Processing Technology, 2025, 272: 108210. [14] AZIZIMEHR B, ARMAGHANI T, GHASEMIASL R, et al. A comprehensive review of recent developments in hydrogen production methods using a new parameter [J]. International Journal of Hydrogen Energy, 2024, 72: 716-29. [15] YUJIA L, BIQI Z, ADENIYI L. Recovery and utilization of crude glycerol, a biodiesel byproduct [J]. RSC advances, 2022, 12(43): 27997-8008. [16] FANGXIA Y, A H M, RUNCANG S. Value-added uses for crude glycerol--a byproduct of biodiesel production [J]. Biotechnology for Biofuels, 2012, 5(1): 13. [17] AWOGBEMI O, DESAI D A. Progress in the conversion of biodiesel-derived crude glycerol into biofuels and other bioproducts [J]. Bioresource Technology Reports, 2025, 30: 102106. [18] WANG H, LI H, LEE C K, et al. A systematic review on utilization of biodiesel-derived crude glycerol in sustainable polymers preparation [J]. International Journal of Biological Macromolecules, 2024, 261(P1): 129536. [19] LIAO M, WANG C, CHEN Y, et al. Self-Reconstruction Mechanism of High-Entropy Oxide in Glycerol Steam Reforming: The Key to H2-rich Syngas Production [J]. ACS Catalysis, 2025, 15(6): 4845-57. [20] MOREIRA R, MORAL A, BIMBELA F, et al. Syngas production via catalytic oxidative steam reforming of glycerol using a Co/Al coprecipitated catalyst and different bed fillers [J]. Fuel Processing Technology, 2019, 189: 120-33. [21] ROSLAN N A, ABIDIN S Z, IDERIS A, et al. A review on glycerol reforming processes over Ni-based catalyst for hydrogen and syngas productions [J]. International Journal of Hydrogen Energy, 2020, 45(36): 18466-89. [22] WANG Y, ZHU S, LU J, et al. Boosting hydrogen production from steam reforming of glycerol via constructing moderate metal-support interaction in Ni@Al2O3 catalyst [J]. Fuel, 2022, 324. [23] WANG Y, LI N, CHEN M, et al. Glycerol steam reforming over hydrothermal synthetic Ni-Ca/attapulgite for green hydrogen generation [J]. Chinese Journal of Chemical Engineering, 2022, 48: 176-90. [24] GUJAR J P, VERMA A, MODHERA B. Optimizing glycerol conversion to hydrogen: A critical review of catalytic reforming processes and catalyst design strategies [J]. International Journal of Hydrogen Energy, 2025, 109: 823-50. [25] WANG Y, CHEN Y, ZHU S, et al. Ni/CeO2 catalysts for glycerol steam reforming: Effect of calcination modes on the catalytic performance [J]. International Journal of Hydrogen Energy, 2024, 65: 804-16. [26] VAIDYA P D, RODRIGUES A E. Glycerol Reforming for Hydrogen Production: A Review [J]. Chemical Engineering & Technology, 2009, 32(10): 1463-9. [27] SCHWENGBER C A, ALVES H J, SCHAFFNER R A, et al. Overview of glycerol reforming for hydrogen production [J]. Renewable and Sustainable Energy Reviews, 2016, 58: 259-66. [28] MACEDO M S, SORIA M A, MADEIRA L M. Process intensification for hydrogen production through glycerol steam reforming [J]. Renewable and Sustainable Energy Reviews, 2021, 146. [29] ALI ZADEH SAHRAEI O, LARACHI F, ABATZOGLOU N, et al. Hydrogen production by glycerol steam reforming catalyzed by Ni-promoted Fe/Mg-bearing metallurgical wastes [J]. Applied Catalysis B: Environmental, 2017, 219: 183-93. [30] CHARISIOU N D, PAPAGERIDIS K N, SIAKAVELAS G, et al. Glycerol Steam Reforming for Hydrogen Production over Nickel Supported on Alumina, Zirconia and Silica Catalysts [J]. Topics in Catalysis, 2017, 60(15-16): 1226-50. [31] DESGAGNéS A, ILIUTA M C. Kinetic study of glycerol steam reforming catalyzed by a Ni-promoted metallurgical residue [J]. Chemical Engineering Journal, 2022, 429. [32] DOU B, SONG Y, WANG C, et al. Hydrogen production from catalytic steam reforming of biodiesel byproduct glycerol: Issues and challenges [J]. Renewable and Sustainable Energy Reviews, 2014, 30: 950-60. [33] FASOLINI A, CESPI D, TABANELLI T, et al. Hydrogen from Renewables: A Case Study of Glycerol Reforming [J]. Catalysts, 2019, 9(9). [34] MACEDO M S, KRALEVA E, EHRICH H, et al. Hydrogen production from glycerol steam reforming over Co-based catalysts supported on La2O3, AlZnOx and AlLaOx [J]. International Journal of Hydrogen Energy, 2022, 47(78): 33239-58. [35] TRAN N H, KANNANGARA G S K. Conversion of glycerol to hydrogen rich gas [J]. Chemical Society Reviews, 2013, 42(24). [36] SUFFREDINI D F P, THYSSEN V V, DE ALMEIDA P M M, et al. Renewable hydrogen from glycerol reforming over nickel aluminate-based catalysts [J]. Catalysis Today, 2017, 289: 96-104. [37] SHU G, LIN Y, WANG S, et al. Dynamic Metal–Support Interaction-Activated Sub-Nanometer Pt Clusters on FeOx Supports for Aqueous Phase Reforming and Hydrogenolysis of Glycerol [J]. ACS Catalysis, 2023, 13(13): 8423-36. [38] ARAQUE M, T L M M, VARGAS J C, et al. Effect of the active metals on the selective H2 production in glycerol steam reforming [J]. Applied Catalysis B: Environmental, 2012, 125: 556-66. [39] CHARISIOU N D, SIAKAVELAS G I, PAPAGERIDIS K N, et al. The Effect of Noble Metal (M: Ir, Pt, Pd) on M/Ce2O3-γ-Al2O3 Catalysts for Hydrogen Production via the Steam Reforming of Glycerol [J]. Catalysts, 2020, 10(7). [40] SENSENI A Z, REZAEI M, MESHKANI F. Glycerol steam reforming over noble metal nanocatalysts [J]. Chemical Engineering Research and Design, 2017, 123: 360-6. [41] CARVALHO D C, SOUZA H S A, FILHO J M, et al. Nanosized Pt-containing Al2O3 as an efficient catalyst to avoid coking and sintering in steam reforming of glycerol [J]. RSC Advances, 2014, 4(106): 61771-80. [42] DEWOOLKAR K D, VAIDYA D P D. Sorption‐Enhanced Steam Reforming of Glycerol over Ni–hydrotalcite: Effect of Promotion with Pt [J]. ChemCatChem, 2016, 8(22): 3499-509. [43] ADHIKARI S, FERNANDO S D, HARYANTO A. Hydrogen production from glycerol: An update [J]. Energy Conversion and Management, 2009, 50(10): 2600-4. [44] MOOGI S, NAKKA L, POTHARAJU S S P, et al. Copper promoted Co/MgO: A stable and efficient catalyst for glycerol steam reforming [J]. International Journal of Hydrogen Energy, 2021, 46(34): 18073-84. [45] FRACCHIA M, ROONGCHAROEN T, CODURI M, et al. Enhancing and understanding the stability of Ni catalysts via In-promotion for the steam reforming of oxygenates: An in-depth operando XRD-XAS and modeling investigation [J]. Applied Catalysis B: Environment and Energy, 2025, 366. [46] YUNZHU W, SONGSHAN Z, SUFANG H, et al. Nanoarchitectonics of Ni/CeO2 Catalysts: The Effect of Pretreatment on the Low-Temperature Steam Reforming of Glycerol [J]. Nanomaterials, 2022, 12(5): 816-. [47] BOBADILLA L F, ROMERO-SARRIA F, CENTENO M A, et al. Promoting effect of Sn on supported Ni catalyst during steam reforming of glycerol [J]. International Journal of Hydrogen Energy, 2016, 41(22): 9234-44. [48] NOR S M-N, ZAINAL A S, ASMAWATI R N, et al. The synergistic role of Ni-Co bimetallic catalyst for H2-rich syngas production via glycerol dry reforming [J]. Journal of the Energy Institute, 2022, 105: 293-308. [49] D. S A, D. Y G. Ni–Cu and Ni–Co Supported on La–Mg Based Metal Oxides Prepared by Coprecipitation and Impregnation for Superior Hydrogen Production via Steam Reforming of Glycerol [J]. Industrial & Engineering Chemistry Research, 2018, 57(14): 4785-97. [50] PAPAGERIDIS K N, SIAKAVELAS G, CHARISIOU N D, et al. Comparative study of Ni, Co, Cu supported on γ-alumina catalysts for hydrogen production via the glycerol steam reforming reaction [J]. Fuel Processing Technology, 2016, 152: 156-75. [51] DANG C, WANG H, YU H, et al. Co-Cu-CaO catalysts for high-purity hydrogen from sorption-enhanced steam reforming of glycerol [J]. Applied Catalysis A, General, 2017, 533: 9-16. [52] FEIJOO J, MACEIRAS R, ALFONSíN V, et al. Influence of Catalytic Support on Hydrogen Production from Glycerol Steam Reforming [J]. Hydrogen, 2025, 6(4). [53] YURDAKUL M, AYAS N, BIZKARRA K, et al. Preparation of Ni-based catalysts to produce hydrogen from glycerol by steam reforming process [J]. International Journal of Hydrogen Energy, 2016, 41(19): 8084-91. [54] CHARISIOU N D, ITALIANO C, PINO L, et al. Hydrogen production via steam reforming of glycerol over Rh/γ-Al2O3 catalysts modified with CeO2 , MgO or La2O3 [J]. Renewable Energy, 2020, 162: 908-25. [55] TIZIANO M, RAKESH S, PIYALI D, et al. Renewable H2 from glycerol steam reforming: effect of La2O3 and CeO2 addition to Pt/Al2O3 catalysts [J]. ChemSusChe, 2010, 3(5): 619-28. [56] MAO Q, GUO Y, LIU X, et al. Identifying the realistic catalyst for aqueous phase reforming of methanol over Pt supported by lanthanum nickel perovskite catalyst [J]. Applied Catalysis B: Environmental, 2022, 313. [57] WANG Y, CHEN Y, ZHU S, et al. Ni/CeO2 catalysts for glycerol steam reforming: Effect of calcination modes on the catalytic performance [J]. International Journal of Hydrogen Energy, 2024, 65: 804-16. [58] WANG X, LI M, LI S, et al. Hydrogen production by glycerol steam reforming with/without calcium oxide sorbent: A comparative study of thermodynamic and experimental work [J]. Fuel Processing Technology, 2010, 91(12): 1812-8. [59] Y A R, B N E, TERRENCE J, et al. Cr and CeO2 promoted Ni/SBA-15 framework for hydrogen production by steam reforming of glycerol [J]. Environmental science and pollution research international, 2023, 30(57): 120945-62. [60] CAKIRYILMAZ N, ARBAG H, OKTAR N, et al. Catalytic performances of Ni and Cu impregnated MCM-41 and Zr-MCM-41 for hydrogen production through steam reforming of acetic acid [J]. Catalysis Today, 2018, 323: 191-9. [61] WANG Y, SUN X, LIANG D, et al. Ethanol steam reforming for hydrogen production over alkali metals modified kaolin-supported Ni catalysts [J]. International Journal of Hydrogen Energy, 2025, 129: 113-29. [62] DAHDAH E, ESTEPHANE J, GENNEQUIN C, et al. Effect of La promotion on Ni/Mg-Al hydrotalcite derived catalysts for glycerol steam reforming [J]. Journal of Environmental Chemical Engineering, 2020, 8(5).