Comparative analysis of aromatic compounds steam reforming over Rh supported on γ-Al₂O₃

Abstract

The steam reforming of bio-oil can provide a sustainable means to produce hydrogen, while tar steam reforming can significantly enhance the efficiency of the biomass gasification process. Bio-oils and tars are highly complex mixtures, and while there has been extensive research on the reforming of small oxygenates and aliphatic hydrocarbons, there have been comparatively much less studies on aromatics reforming. In the current work, we present a comparative study of the steam reforming of hydroquinone, benzyl alcohol and toluene, selected as model compounds of the aromatic fraction of bio-oils and tars with different functional groups. The effect of temperature, partial pressure of reactants, and contact time is studied over a Rh catalyst supported on γ-Al₂O₃. Across the range of conditions studied, hydroquinone is found to be more reactive, followed by benzyl alcohol, and, lastly, toluene. The differences are attributed to the presence of hydroxyl groups in the case of the former two compounds, versus a methyl group in the case of toluene, effectively correlating activity with the O/C ratio in the compounds’ molecule. Nonetheless, similar pathways are observed, with methane, benzene, naphthalene and toluene (during hydroquinone and benzyl alcohol reforming) detected as products in addition to carbon oxides and hydrogen.

Graphical abstract

Keywords

hydroquinone / benzyl alcohol / toluene / steam reforming / hydrogen production / rhodium

References

[1] Abou Rjeily M , Gennequin C , Pron H , Abi-Aad E , Randrianalisoa J H . Pyrolysis-catalytic upgrading of bio-oil and pyrolysis-catalytic steam reforming of biogas: a review. Environmental Chemistry Letters, 2021, 19(4): 2825–2872

[2] Abdelaal A , Antolini D , Piazzi S , Patuzzi F , Villot A , Gerente C , Baratieri M . Steam reforming of tar using biomass gasification char in a pilot-scale gasifier. Fuel, 2023, 351: 128898

[3] Chen W H , Biswas P P , Ong H C , Hoang A T , Nguyen T B , Di Dong C . A critical and systematic review of sustainable hydrogen production from ethanol/bioethanol: steam reforming, partial oxidation, and autothermal reforming. Fuel, 2023, 333: 126526

[4] Pafili A , Charisiou N D , Douvartzides S L , Siakavelas G I , Wang W , Liu G , Papadakis V G , Goula M A . Recent progress in the steam reforming of bio-oil for hydrogen production: a review of operating parameters, catalytic systems and technological innovations. Catalysts, 2021, 11(12): 1526

[5] Santamaria L , Lopez G , Fernandez E , Cortazar M , Arregi A , Bilbao J . Progress on catalyst development for the steam reforming of biomass and waste plastics pyrolysis volatiles: a review. Energy & Fuels, 2021, 35(21): 17051–17084

[6] 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

[7] Mei D , Lebarbier V M , Rousseau R , Glezakou V A , Albrecht K O , Kovarik L , Flake M , Dagle R A . Comparative investigation of benzene steam reforming over spinel supported Rh and Ir catalysts. ACS Catalysis, 2013, 3(6): 1133–1143

[8] Trinh Q T , Nguyen A V , Huynh D C , Pham T H , Mushrif S H . Mechanistic insights into the catalytic elimination of tar and the promotional effect of boron on it: first-principles study using toluene as a model compound. Catalysis Science & Technology, 2016, 6(15): 5871–5883

[9] Mukai D , Murai Y , Higo T , Tochiya S , Hashimoto T , Sugiura Y , Sekine Y . In situ IR study for elucidating reaction mechanism of toluene steam reforming over Ni/La_0.7Sr_0.3AlO_3−δ catalyst. Applied Catalysis A: General, 2013, 466: 190–197

[10] Oemar U , Ming Li A , Hidajat K , Kawi S . Mechanism and kinetic modeling for steam reforming of toluene on La_0.8Sr_0.2Ni_0.8Fe_0.2O₃ catalyst. AIChE Journal. American Institute of Chemical Engineers, 2014, 60(12): 4190–4198

[11] Łamacz A . Toluene steam reforming over Ni/CeZrO₂—the influence of steam to carbon ratio and contact time on the catalyst performance and carbon deposition. Catalysts, 2022, 12(2): 219

[12] Sayas S , Vivó N , Da Costa-Serra J F , Chica A . Toluene steam reforming over nickel based catalysts. International Journal of Hydrogen Energy, 2021, 46(33): 17472–17480

[13] Meng J , Zhao Z , Wang X , Chen J , Zheng A , Huang Z , Wei G , Li H . Steam reforming and carbon deposition evaluation of phenol and naphthalene used as tar model compounds over Ni and Fe olivine-supported catalysts. Journal of the Energy Institute, 2019, 92(6): 1765–1778

[14] Xu X , Friend C M . The Role of coverage in determining adsorbate stability: phenol reactivity on Rh(111). Journal of Physical Chemistry, 1989, 93(24): 8072–8080

[15] Honkela M L , Björk J , Persson M . Computational study of the adsorption and dissociation of phenol on Pt and Rh surfaces. Physical Chemistry Chemical Physics, 2012, 14(16): 5849–5854

[16] Garcia-Pintos D , Voss J , Jensen A D , Studt F . Hydrodeoxygenation of phenol to benzene and cyclohexane on Rh(111) and Rh(211) surfaces: insights from density functional theory. Journal of Physical Chemistry C, 2016, 120(33): 18529–18537

[17] Zhurka M D , McCue A J , Kechagiopoulos P N . Reaction pathways of phenol steam reforming over Rh and Ni-Co based catalysts supported on γ-Al₂O₃. Fuel, 2024, 364: 131102

[18] Pan Z , Puente-Urbina A , Bodi A , van Bokhoven J A , Hemberger P . Isomer-dependent catalytic pyrolysis mechanism of the lignin model compounds catechol, resorcinol and hydroquinone. Chemical Science, 2021, 12(9): 3161–3169

[19] Yang H , Furutani Y , Kudo S , Hayashi J , Norinaga K . Experimental investigation of thermal decomposition of dihydroxybenzene isomers: catechol, hydroquinone, and resorcinol. Journal of Analytical and Applied Pyrolysis, 2016, 120: 321–329

[20] Xie W , Zhang Y , Zhang Y , Liu C , Wang Y , Xie Y , Ji G , Li A . Fast pyrolysis of biomass with diverse properties to produce liquid hydrogen storage molecules. Carbon Capture Science & Technology, 2024, 12: 100230

[21] Fenton D M , Fett E R , Schluter E C . Noble metal catalysis. IV. Products from benzyl alcohol decomposition. Journal of Applied Chemistry & Biotechnology, 1977, 27(1): 281–290

[22] Pu J , Toyoda T , Qian E W . Evaluation of reactivities of various compounds in steam reforming over RuNi/BaOAl₂O₃ catalyst. Energy & Fuels, 2018, 32(2): 1804–1811

[23] Zhang M , Wang M , Xu B , Ma D . How to measure the reaction performance of heterogeneous catalytic reactions reliably. Joule, 2019, 3(12): 2876–2883

[24] Inukai J , Wakisaka M , Yamagishi M , Itaya K . Adlayer of hydroquinone on Rh(111) in solution and in vacuum studied by STM and LEED. Journal of the Electrochemical Society, 2005, 152(2): E35–E39

[25] Ioannides T , Verykios X E . The interaction of benzene and toluene with Rh dispersed on SiO₂, Al₂O₃, and TiO₂ carriers. Journal of Catalysis, 1993, 143(1): 175–186

[26] Inukai J , Wakisaka M , Itaya K . An STM study on the growth process of vapor-deposited hydroquinone adlayers on Rh(111) and Pt(111). Chemical Physics Letters, 2004, 399: 373–377

[27] Jia X , An W . Adsorption of monocyclic aromatics on transition metal surfaces: insight into variation of binding strength from first-principles. Journal of Physical Chemistry C, 2018, 122(38): 21897–21909

[28] Aubert C , Durand R , Geneste P , Moreau C . Factors affecting the hydrogenation of substituted benzenes and phenols over a sulfided NiO-MoO₃γ-Al₂O₃ catalyst. Journal of Catalysis, 1988, 112(1): 12–20

[29] Hu X , Lu G . Investigation of the steam reforming of a series of model compounds derived from bio-oil for hydrogen production. Applied Catalysis B: Environmental, 2009, 88(3–4): 376–385

[30] Zhang Z , Liu L , Shen B , Wu C . Preparation, modification and development of Ni-based catalysts for catalytic reforming of tar produced from biomass gasification. Renewable & Sustainable Energy Reviews, 2018, 94: 1086–1109

[31] Li Y , Zhang L , Zhang Z , Liu Q , Zhang S , Liu Q , Hu G , Wang Y , Hu X . Steam reforming of the alcohols with varied structures: impacts of acidic sites of Ni catalysts on coking. Applied Catalysis A: General, 2019, 584: 117162–117181

[32] Zhou J , Mullins D R . Rh-promoted methanol decomposition on cerium oxide thin films. Journal of Physical Chemistry B, 2006, 110(32): 15994–16002

[33] Dufour A , Masson E , Girods P , Rogaume Y , Zoulalian A . Evolution of aromatic tar composition in relation to methane and ethylene from biomass pyrolysis-gasification. Energy & Fuels, 2011, 25(9): 4182–4189

[34] Silveira E B , Rabelo-Neto R C , Noronha F B . Steam reforming of toluene, methane and mixtures over Ni/ZrO₂ catalysts. Catalysis Today, 2017, 289: 289–301

[35] Hu X , Lu G . Investigation of the effects of molecular structure on oxygenated hydrocarbon steam re-forming. Energy & Fuels, 2009, 23(2): 926–933

[36] Török B , Pálinkó I , Molnár Á , Bartók M . Ring enlargement and aromatization of propylcyclobutane over silica-supported Pt, Pd and Rh in hydrogen atmosphere. Journal of Molecular Catalysis, 1994, 91(1): 61–69

[37] Liu G , Zhao Y , Guo J . High selectively catalytic conversion of lignin-based phenols into para-/m-xylene over Pt/HZSM-5. Catalysts, 2016, 6(2): 19

[38] González C , Marín P , Díez F V , Ordóñez S . Gas-phase hydrodeoxygenation of benzaldehyde, benzyl alcohol, phenyl acetate, and anisole over precious metal catalysts. Industrial & Engineering Chemistry Research, 2016, 55(8): 2319–2327

[39] Moldoveanu S C . Pyrolysis of hydrocarbons. Techniques and Instrumentation in Analytical Chemistry, 2010, 28: 131–229

[40] MoldoveanuS C. Pyrolysis of Organic Molecules. 2nd ed. Amsterdam: Elsevier, 2019, 35–161

[41] Buckingham G T , Porterfield J P , Kostko O , Troy T P , Ahmed M , Robichaud D J , Nimlos M R , Daily J W , Ellison G B . The thermal decomposition of the benzyl radical in a heated micro-reactor. II. Pyrolysis of the tropyl radical. Journal of Chemical Physics, 2016, 145(1): 014305

[42] Tao J , Zhao L , Dong C , Lu Q , Du X , Dahlquist E . Catalytic steam reforming of toluene as a model compound of biomass gasification tar using Ni-CeO₂/SBA-15 catalysts. Energies, 2013, 6(7): 3284–3296

[43] Korotvicka A , Necas D , Kotora M . Rhodium-catalyzed C–C bond cleavage reactions—an update. Current Organic Chemistry, 2012, 16(10): 1170–1214

[44] Brown N F , Barteau M A . Reactions of 1-propanol and propionaldehyde on Rh(111). Langmuir, 1992, 8(3): 862–869

[45] Papavasiliou J , Avgouropoulos G , Ioannides T . Combined steam reforming of methanol over Cu-Mn spinel oxide catalysts. Journal of Catalysis, 2007, 251(1): 7–20

[46] Garbarino G , Wang C , Valsamakis I , Chitsazan S , Riani P , Finocchio E , Flytzani-Stephanopoulos M , Busca G . A study of Ni/Al₂O₃ and Ni-La/Al₂O₃ catalysts for the steam reforming of ethanol and phenol. Applied Catalysis B: Environmental, 2015, 174–175: 21–34

[47] Blades H , Blades A T , Steacie E W R . The kinetics of the pyrolysis of toluene. Canadian Journal of Chemistry, 1954, 32(3): 298–311

[48] Duong N N , Aruho D , Wang B , Resasco D E . Hydrodeoxygenation of anisole over different Rh surfaces. Chinese Journal of Catalysis, 2019, 40(11): 1721–1730

[49] Chu T C , Buras Z J , Smith M C , Uwagwu A B , Green W H . From benzene to naphthalene: direct measurement of reactions and intermediates of phenyl radicals and acetylene. Physical Chemistry Chemical Physics, 2019, 21(40): 22248–22258

[50] Lukyanov D B , Vazhnova T . Selective and stable benzene alkylation with methane into toluene over PtH-MFI bifunctional catalyst. Journal of Molecular Catalysis A: Chemical, 2009, 305(1–2): 95–99

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The Author(s) 2025. This article is published with open access at link.springer.com and journal.hep.com.cn