Abstract
In this paper, the application of molecular catalysis for steam reforming of ethanol (SRE) is reviewed. Eight metals (Ni, Co, Cu, Pt, Rh, Pd, Ir and Ru) have shown high catalytic activity for SRE. Among them Ni and Rh are very promising because of high d character in the metal bond and low metal-oxygen bonding (vs. metal-carbon). They can effectively promote C-C bond cleavage in the rate-determining process during SRE. However, Rh is weak in water-gas-shift so that CH4 and CO become the main by-products at low reaction temperatures, while Ni catalysts suffer from rapid deactivation due to coking and sintering. Two low-temperature CO-free catalysts have been developed in our lab, namely Rh-Fe/Ca-Al2O3 and carbonyl-derived Rh-Co/CeO2, in which the presence of iron oxide or Co can promote water-gas-shift reaction and significantly improve the SRE performance. On the other hand, adding 3 wt% CaO to Ni/Al2O3 can greatly improve the catalyst stability because the Ca modification not only increases Ni concentration on the Ni/Ca-Al2O3 surface and 3d valence electron density, but also facilitates the water adsorption and coke gasification via water-gas-shift. The availability of abundant surface OH groups helps the formation and conversion of adsorbed formate intermediate. Hence, ethanol reaction on Ca-Al2O3-supported Ni, Pt, Pd and Rh catalysts are found to follow the formate-intermediated pathway, a new reaction pathway alternative to the traditional acetate-intermediated pathway.
Similar content being viewed by others
References
Note: If 1 liter of pure ethanol (density 0.79 g/mL) is used directly as a fuel of heat engines, only about 20% of the chemical energy stored in ethanol can be converted to useful mechanical work. This will generate 4392 kJ of energy (per liter) by assuming the enthalpy of combustion is 1277 kJ/mol for ethanol. On the other hand, 1 liter of ethanol can be converted to 92.85 mole of H2 (assuming 90% H2 selectivity in SRE) and will produce 12829 kJ energy (assuming 60% the fuel cell efficiency).
Sun J, Wang Y. Recent advances in catalytic conversion of ethanol to chemicals. ACS Catal, 2014, 4: 1078–1090
Kumar A, Prasad R, Sharma YC. Steam reforming of ethanol: production of renewable hydrogen. Int J Environ Res Dev, 2014, 4: 203–212
Mattos LV, Jacobs G, Davis BH, Noronha FB. Production of hydrogen from ethanol: review of reaction mechanism and catalyst deactivation. Chem Rev, 2012, 112: 4094–4123
Trane R, Dahl S, Skjoth-Rasmussen MS, Jensen AD. Catalytic steam reforming of bio-oil. Int J Hydrogen Energy, 2012, 37: 6447–6472
Ni M, Leung DYC, Leung MKH. A review on reforming bio-ethanol for hydrogen production Int J Hydrogen Energy, 2007, 32: 3238–3247
Vaidya PD, Rodrigues AE. Insight into steam reforming of ethanol to produce hydrogen for fuel cells. Chem Eng J, 2006, 117: 38–49
Davda PR, Shabaker JW, Huber GW, Cortrighti RD, Dumesic JA. A review of catalytic issues and process conditions for renewable hydrogen and alkanes by aqueous-phase reforming of oxygenated hydrocarbons over supported metal catalysts Appl Catal B, 2005, 56: 171–176
Haryanto A, Fernando S, Murali N, Adhikari S. Current status of hydrogen production techniques by steam reforming of ethanol: a review. Energy Fuels, 2005, 19: 2098–2106
Koh ACW, Leong WK, Chen L, Ang TP, Lin J, Johnson BFG, Khimyak T. Highly efficient ruthenium and ruthenium-platinum cluster-derived nanocatalysts for hydrogen production via ethanol steam reforming. Catal Commun, 2008, 9: 170–175
Zhong ZY, Ang H, Choong CKS, Chen L, Huang L, Lin J. The role of acidic sites and the catalytic reaction pathways on the Rh/ZrO2 catalysts for ethanol steam reforming. Phys Chem Chem Phys, 2009, 11: 872–880
Huang L, Choong CKS, Chen L, Wang Z, Zhong Z, Cuerva CC, Lin J. Monometallic carbonyl-derived CeO2-supported Rh and Co bicomponent catalysts for CO-free, high-yield H2 generation from low-temperature ethanol steam reforming. ChemCatChem, 2013, 5: 220–234
Chen L, Choong CKS, Zhong Z, Huang L, Ang TP, Hong L, Lin J. Carbon monoxide-free hydrogen production via low-temperature steam reforming of ethanol over iron-promoted Rh catalyst. J Catal, 2010, 276: 197–200
Choong CKS, Chen L, Du Y, Wang Z, Hong L, Borgna A. Rh-Fe/Ca-Al2O3: a unique catalyst for CO-free hydrogen production in low temperature ethanol steam reforming. Top Catal, 2014, 57: 627–636
Choong CKS, Huang L, Zhong Z, Lin J, Hong L, Chen L. Effect of calcium addition on catalytic ethanol steam reforming of Ni/Al2O3: II. Acidity/basicity, water adsorption and catalytic activity. Appl Catal A: General, 2011, 407: 155–162
Choong CKS, Zhong Z, Huang L, Wang Z, Ang TP, Borgna A, Lin J, Hong L, Chen L. Effect of calcium addition on catalytic ethanol steam reforming of Ni/Al2O3: I. Catalytic stability, electronic properties and coking mechanism. Appl Catal A: General, 2011, 407: 145–154
Chen L, Choong CKS, Zhong Z, Huang L, Wang Z, Lin J. Support and alloy effects on activity and product selectivity for ethanol steam reforming over supported nickel cobalt catalysts. Int J Hydrogen Energy, 2012, 37: 16321–16332
Choong CKS, Zhong Z, Huang L, Borgna A, Hong L, Chen L, Lin J. Infrared evidence of a formate-intermediate mechanism over Ca-modified supports in low-temperature ethanol steam reforming. ACS Catal, 2014, 4: 2359–2363
Lin J, Neoh KG, Teo WKJ. Thermogravimetry-FTIR study of the surface formate decomposition on Cu, CuCl, Cu2O and CuO correlations between reaction selectivity and structural properties. Chem Soc, Faraday Trans, 1994, 9: 355–362
Fishtik I, Alexander A, Datta R, Geana D. A thermodynamic analysis of hydrogen production by steam reforming of ethanol via response reactions. Int J Hydrogen Energy, 2000, 25: 31–45
Garcia EY, Laborde MA. Hydrogen production by the steam reforming of ethanol: thermodynamic analysis. Int J Hydrogen Energy, 1991, 16: 16–307
Vasudeva K, Mitra N, Umansankar P, Dhingra SC. Steam reforming of ethanol for hydrogen production: thermodynamic analysis. Int J Hydrogen Energy, 1996, 21: 13–18
Vaidya PD, Rodrigues AE. Insight into steam reforming of ethanol to produce hydrogen for fuel cells. Chem Eng, 2006, 17: 39–49
Singhto W, Laosiripojana N, Assabumrungrat S, Charojrochkul S. Steam reforming of bio-ethanol over Ni on Ce-ZrO2 support: influence of redox properties on the catalyst reactivity. Songklanakarin J Sci Technol, 2006, 28: 1251–1264
Llorca J, Piscina PR de la, Sales J. Homs direct production of hydrogen from ethanolic aqueous solutions over oxidecatalysts N. Chem Commun, 2001: 641–642
Llorca J, Piscina PR de la, Dalmon JA, Sales J, Homs N. CO-free hydrogen from steam-reforming of bioethanol over ZnO-supported cobalt catalysts effect of the metallic precursor. Appl Catal B, 2003, 43: 355–369
Llorca J, Homs N, Piscina PR de la. In situ DRIFT-mass spectrometry study of the ethanol steam-reforming reaction over carbonyl-derived Co/ZnO catalysts. J Catal, 2004, 27: 556–560
Vecchietti J, Bonivardi A, Xu W, Stacchiola D, Delgado JJ, Calatayud M, Collins SnE. Understanding the role of oxygen vacancies in the water gas shift reaction on ceria-supported platinum catalysts. ACS Catal, 2014, 4: 2088–2096
Llorca L, Homs N, Sales J, Piscin PR de la. Efficient production of hydrogen over supported cobalt catalysts from ethanol steam reforming. J Catal, 2002, 209: 306–317
Wang Z, Wang H, Liu Y. La1−x CaxFe1−x CoxO3: a stable catalyst for oxidative steam reforming of ethanol to produce hydrogen. RSC Adv, 2013, 3: 10027–10036
Xu W, Liu Z, Johnston-Peck AC, Senanayake SD, Zhou G, Stacchiola D, Stach EA, Rodriguez JA. Steam reforming of ethanol on Ni/CeO2: reaction pathway and interaction between Ni and the CeO2 support. ACS Catal, 2013, 3: 975–984
Cavallaro S. Ethanol steam reforming on Rh/Al2O3 catalysts. Energ Fuel, 2000, 14: 1195–1199
Duan S, Senkan S. Catalytic conversion of ethanol to hydrogen using combinatorial methods. Ind Eng Chem Res, 2005, 44: 6381–6386
Auprêtre F, Descorme C, Duprez D. Bio-ethanol catalytic steam reforming over supported metal catalysts. Catal Comm, 2002, 3: 263–267
Liguras DK, Kondarides DI, Verykios XE. Production of hydrogen for fuel cells by steam reforming of ethanol over supported noble metal catalysts. Appl Catal B, 2003, 43: 345–354
Basagiannis AC, Panagiotopoulou P, Verykios XE. Low temperature steam reforming of ethanol over supported noble metal catalysts. Top Catal, 2008, 51: 2–12
Frusteri F, Freni S, Spadaro L, Chiodo V, Bonura G, Donato S, Cavallaro S. H2 production for MC fuel cell by steam reforming of ethanol over MgO supported Pd, Rh, Ni and Co catalysts. Catal Commun, 2004, 5: 611–615
Idriss H. Ethanol reactions over the surfaces of noble metal/cerium oxide catalysts. Platin Met Rev, 2004, 48: 105–115
Ferrin P, Simonetti D, Kandoi S, Kunkes E, Dumesic JA, Nørskov JK, Mavrikakis M. Modeling ethanol decomposition on transition metals: a combined application of scaling and Brønsted-Evans-Polanyi relations. J Am Chem Soc, 2009, 131: 5809–5815
Mavrikakis M, Barteau MA. Oxygenate reaction pathways on transition metal surfaces. J Mol Catal A: Chem, 1998, 131: 135–147
Sinfelt JH, Yates JC. Catalytic hydrogenolysis of ethane over noble metals of Group VIII. J Catal, 1967, 8: 85–90
Sinfelt JH, Taylor WF, Yates DJC. Catalysis over supported metals. III. Comparison of metals of known surface area for ethane hydrogenolysis. J Phys Chem, 1965, 69: 95–101
Gates SM, Russell JN, Yates Jr JT. Bond activation sequence observed in the chemisorption and surface reaction of ethanol on Ni(111). Surf Sci, 1986, 171: 111–134
Maírikakis M, Barteaur MA. Oxygenate reaction pathways on transition metal surfaces. J Mol Catal A: Chem, 1998, 131: 135–147
Davis L, Barteau MA. The influence of oxygen on the selectivity of alcohol conversion on Pd(111) surface. Sur Sci, 1988, 197: 123–152
Alcalá R, Mavrikakis M, Dumesic JA. DFT studies for cleavage of C-C and C-O bonds in surface species derived from ethanol on Pt(111). J Catal, 2003, 218: 178–190
Morton D, Cole-Hamilton DJ, Utuk ID, Paneque-Sosa M, Manuel L. Hydrogen production from ethanol catalysed by Group 8 metal complexes. J Chem Soc, Dalton Trans, 1989, 3: 489–495
Deluga GA, Salge JR, Schmidt LD, Verykios XE. Renewable hydrogen from ethanol by autothermal reforming. Science, 2004, 303: 993–997
Ferencz Zs, Erdohelyi A, Baan K, Oszko A, Ovari L, Konya Z, Papp C, Steinruck HP, Kiss J. Effects of support and Rh additive on Co-based catalysts in the ethanol steam reforming reaction. ACS Catal, 2014, 4: 1205–1218
Senanayake SD, Evans J, Agnoli S, Barrio L, Chen TL, Hrbek J, Rodriguez JA. Water-gas shift and CO methanation reactions over Ni-CeO2(111) catalysts. Top Catal, 2011, 54: 34–41 Han X, Yu Y, He H, Shan W. Hydrogen production from oxidative steam reforming of ethanol over rhodium catalysts supported on Ce-La solid solution. Int J Hydrogen Energy, 2013, 38: 10293–10304
Aupretre F, Descorme C, Duprez D, Casanave D, Uzio D. Ethanol steam reforming over MgxNi1−x Al2O3 spinel oxide-supported Rh catalysts. J Catal, 2005, 233: 464–477
Duprez D. Selective steam reforming of aromatic compounds on metal catalysts. Appl Catal A: Gen, 1992, 82: 111–157
Martin D, Duprez D. Mobility of surface species on oxides. 1. Isotopic exchange of 18O2 with 16O of SiO2, Al2O3, ZrO2, MgO, CeO2, and CeO2-Al2O3. Activation by noble metals. Correlation with oxide basicity. J Phys Chem, 1996, 100: 9429–9438
Rostrup-Nielsen JR. Activity of nickel catalysts for steam reforming of hydrocarbons. J Catal, 1973, 31: 173–199
Sutton JE, Panagiotopoulou P, Verykios XE, Vlachos DG. Combined DFT. Micro-kinetic, and experimental study of ethanol steam reforming on Pt. J Phys Chem C, 2013, 117: 4691–4706
Panagiotopoulou P, Verykios XE. Mechanistic aspects of the low temperature steam reforming of ethanol over supported Pt catalysts. Int J Hydrogen Energ, 2012, 37: 16333–16345
Sanchez-Sanchez MC, Yerga RMN, Kondarides DI, Verykios XE, Fierro JLG. Mechanistic aspects of the ethanol steam reforming reaction for hydrogen production on Pt, Ni, and Pt-Ni catalysts supported on γ-Al2O3. J Phys Chem A, 2010, 114: 3873–3882
Yee A, Morrison SJ, Idriss H. A study of ethanol reaction over Pt/CeO2 by temperature-programmed desorption and in situ FT-IR spectroscopy: evidence of benzene formation. J Catal, 2000, 191: 30–45
Erdohelyi A, Raskó J, Kecskés T, Tóth M, Domok M, Baañ K. Hydrogen formation in ethanol reforming on supported noble metal catalysts. Catal Today, 2006, 116: 367–376
Kagel RO. Infrared investigation of the adsorption and surface reactions of the C1 through C4 normal alcohols on γ-alumina. J Phys Chem, 1967, 71: 844–850
Kagel RO, Greenler RG. Infrared study of the adsorption of methanol and ethanol on magnesium oxide. J Chem Phys, 1968, 49: 1638–1647
Yee A, Morrison SJ, Idriss H. A study of the reaction of ethanol on CeO2 and Pd/CeO2 by steady state react ions, TPD and in-situ FT-IR. J Catal, 1999, 186: 279–295
Author information
Authors and Affiliations
Corresponding authors
Rights and permissions
About this article
Cite this article
Lin, J., Chen, L., Choong, C.K.S. et al. Molecular catalysis for the steam reforming of ethanol. Sci. China Chem. 58, 60–78 (2015). https://doi.org/10.1007/s11426-014-5262-0
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11426-014-5262-0