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Licensed Unlicensed Requires Authentication Published by De Gruyter September 1, 2018

Study of Process Factor Effects and Interactions in Synthesis Gas Production via a Simulated Model for Glycerol Steam Reforming

Adewale George Adeniyi and Joshua O. Ighalo


With the continual global focus in biodiesel production, a glut of glycerol (it’s by-product) is expected in the world market. One viable and proven possibility in utilising the less useful and desired glycerol as a source for the production of hydrogen via the steam reforming and water gas shift process. This study is essentially and in-depth investigation of the interaction of the key process factors and their effect on the selectivity of Hydrogen from the process. The basis of the investigation was a simulated model of the steam reforming process using ASPEN plus V8.8. Results were obtained according to the optimisation plan developed using central composite design (CCD). The variables (and range) were temperature (700 0c – 1100 0c), Pressure (0.1 atm – 1.9 atm) and steam to glycerol ratio (1 mol/mol – 12 mol/mol). The results of optimisation showed that maximum yield of H2 and minimal methanation can be obtained at a temperature of 900 0c, an STGR of 15.75 mol/mol and at atmospheric pressure. The optimum result was predicted by the simulation as H2 = 66.72 %, CO = 11.76 %, CO2 = 21.52 % and CH4 = 0 %. Sensitivity analysis was carried out to show that Hydrogen production is favoured at higher temperatures and methanation at lower temperatures respectively. A critical investigation of the factor effects and interactions for each product in the synthesis gas (dry basis) was also carried out using response surface methodology.


[1] Dou B, Song Y, Wang C, Chen H, Xu Y. Hydrogen production from catalytic steam reforming of biodiesel byproduct glycerol: issues and challenges. Renewable and Sustainable Energy Reviews. 2014;30:950–60.10.1016/j.rser.2013.11.029Search in Google Scholar

[2] Adhikari S, Fernando SD, Haryanto A. Hydrogen production from glycerin by steam reforming over nickel catalysts. Renewable Energy. 2008;33:1097–100.10.1016/j.renene.2007.09.005Search in Google Scholar

[3] Adhikari S, Fernando S, Haryanto A. A comparative thermodynamic and experimental analysis on hydrogen production by steam reforming of glycerin. Energy & Fuels. 2007a;21:2306–10.10.1021/ef070035lSearch in Google Scholar

[4] Slinn M, Kendall K, Mallon C, Andrews J. Steam reforming of biodiesel by-product to make renewable hydrogen. Bioresour Technol. 2008;99:5851–58.10.1016/j.biortech.2007.10.003Search in Google Scholar

[5] Adhikari S, Fernando SD, To SF, Bricka RM, Steele PH, Haryanto A. Conversion of glycerol to hydrogen via a steam reforming process over nickel catalysts. Energy & Fuels. 2008;22:1220–26.10.1021/ef700520fSearch in Google Scholar

[6] Chattanathan SA, Adhikari S, Abdoulmoumine N. A review on current status of hydrogen production from bio-oil. Renewable and Sustainable Energy Reviews. 2012;16:2366–72.10.1016/j.rser.2012.01.051Search in Google Scholar

[7] Fu P, Yi W, Li Z, Bai X, Zhang A, Li Y, et al. Investigation on hydrogen production by catalytic steam reforming of maize stalk fast pyrolysis bio-oil. Int J Hydrogen Energy. 2014;39:13962–71.10.1016/j.ijhydene.2014.06.165Search in Google Scholar

[8] Wang D, Czernik S, Montane D, Mann M, Chornet E. Biomass to hydrogen via fast pyrolysis and catalytic steam reforming of the pyrolysis oil or its fractions. Ind Eng Chem Res. 1997;36:1507–18.10.1021/ie960396gSearch in Google Scholar

[9] Adhikari S, Fernando S, Haryanto A. Production of hydrogen by steam reforming of glycerin over alumina-supported metal catalysts. Catal Today. 2007b;129:355–64.10.1016/j.cattod.2006.09.038Search in Google Scholar

[10] Haryanto A, Fernando S, Murali N, Adhikari S. Current status of hydrogen production techniques by steam reforming of ethanol: a review. Energy & Fuels. 2005;19:2098–106.10.1021/ef0500538Search in Google Scholar

[11] Hajjaji N, Chahbani A, Khila Z, Pons M-N. A comprehensive energy–exergy-based assessment and parametric study of a hydrogen production process using steam glycerol reforming. Energy. 2014;64:473–83.10.1016/ in Google Scholar

[12] Adhikari S, Fernando S, Gwaltney SR, To SF, Bricka RM, Steele PH, et al. A thermodynamic analysis of hydrogen production by steam reforming of glycerol. Int J Hydrogen Energy. 2007;32:2875–80.10.1016/j.ijhydene.2007.03.023Search in Google Scholar

[13] Chen H, Zhang T, Dou B, Dupont V, Williams P, Ghadiri M, et al. Thermodynamic analyses of adsorption-enhanced steam reforming of glycerol for hydrogen production. Int J Hydrogen Energy. 2009;34:7208–22.10.1016/j.ijhydene.2009.06.070Search in Google Scholar

[14] Da Silva AL, Müller IL. Hydrogen production by sorption enhanced steam reforming of oxygenated hydrocarbons (ethanol, glycerol, n-butanol and methanol): thermodynamic modelling. Int J Hydrogen Energy. 2011;36:2057–75.10.1016/j.ijhydene.2010.11.051Search in Google Scholar

[15] Patel M, Jindal TK, Pant KK. Kinetic study of steam reforming of ethanol on Ni-based ceria–zirconia catalyst. Ind Eng Chem Res. 2013;52:15763–71.10.1021/ie401570sSearch in Google Scholar

[16] Wang X, Li S, Wang H, Liu B, Ma X. Thermodynamic analysis of glycerin steam reforming. Energy & Fuels. 2008;22:4285–91.10.1021/ef800487rSearch in Google Scholar

[17] Wang X, Wang N, Li M, Li S, Wang S, Ma X. Hydrogen production by glycerol steam reforming with in situ hydrogen separation: a thermodynamic investigation. Int J Hydrogen Energy. 2010;35:10252–56.10.1016/j.ijhydene.2010.07.140Search in Google Scholar

[18] 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;36:2120–27.10.1016/j.renene.2011.01.022Search in Google Scholar

[19] Yenumala SR, Maity SK. Reforming of vegetable oil for production of hydrogen: a thermodynamic analysis. Int J Hydrogen Energy. 2011;36:11666–75.10.1016/j.ijhydene.2011.06.055Search in Google Scholar

[20] Dou B, Dupont V, Rickett G, Blakeman N, Williams PT, Chen H, et al. Hydrogen production by sorption-enhanced steam reforming of glycerol. Bioresour Technol. 2009;100:3540–47.10.1016/j.biortech.2009.02.036Search in Google Scholar

[21] Adhikari S, Fernando SD, Haryanto A. Kinetics and reactor modeling of hydrogen production from glycerol via steam reforming process over Ni/CeO2 catalysts. Chem Eng Technol. 2009;32:541–47.10.1002/ceat.200800462Search in Google Scholar

[22] Cheng CK, Foo SY, Adesina AA. H2-rich synthesis gas production over Co/Al2O3 catalyst via glycerol steam reforming. Catal Commun. 2010;12:292–98.10.1016/j.catcom.2010.09.018Search in Google Scholar

[23] Chiodo V, Freni S, Galvagno A, Mondello N, Frusteri F. Catalytic features of Rh and Ni supported catalysts in the steam reforming of glycerol to produce hydrogen. Appl Catalysis A: Gen. 2010;381:1–7.10.1016/j.apcata.2010.03.039Search in Google Scholar

[24] Dave CD, Pant K. Renewable hydrogen generation by steam reforming of glycerol over zirconia promoted ceria supported catalyst. Renewable Energy. 2011;36:3195–202.10.1016/j.renene.2011.03.013Search in Google Scholar

[25] Hirai T, Ikenaga N-O, Miyake T, Suzuki T. Production of hydrogen by steam reforming of glycerin on ruthenium catalyst. Energy & Fuels. 2005;19:1761–62.10.1021/ef050121qSearch in Google Scholar

[26] Nichele V, Signoretto M, Menegazzo F, Gallo A, Dal Santo V, Cruciani G, et al. Glycerol steam reforming for hydrogen production: design of Ni supported catalysts. Appl Catalysis B: Environ. 2012;111:225–32.10.1016/j.apcatb.2011.10.003Search in Google Scholar

[27] Pompeo F, Santori G, Nichio NN. Hydrogen and/or syngas from steam reforming of glycerol. Study of platinum catalysts. Int J Hydrogen Energy. 2010;35:8912–20.10.1016/j.ijhydene.2010.06.011Search in Google Scholar

[28] Profeti LP, Ticianelli EA, Assaf EM. Production of hydrogen via steam reforming of biofuels on Ni/CeO2–al2O3 catalysts promoted by noble metals. Int J Hydrogen Energy. 2009;34:5049–60.10.1016/j.ijhydene.2009.03.050Search in Google Scholar

[29] Zhang B, Tang X, Li Y, Xu Y, Shen W. Hydrogen production from steam reforming of ethanol and glycerol over ceria-supported metal catalysts. Int J Hydrogen Energy. 2007;32:2367–73.10.1016/j.ijhydene.2006.11.003Search in Google Scholar

[30] Dou B, Dupont V, Williams PT. Computational fluid dynamics simulation of gas− solid flow during steam reforming of glycerol in a fluidized bed reactor. Energy & Fuels. 2008;22:4102–08.10.1021/ef8002679Search in Google Scholar

[31] Dou B, Song Y. A CFD approach on simulation of hydrogen production from steam reforming of glycerol in a fluidized bed reactor. Int J Hydrogen Energy. 2010;35:10271–84.10.1016/j.ijhydene.2010.07.165Search in Google Scholar

[32] Licker DM. Dictionary of engineering. 2nd ed. Chicago: Mc-Graw Hill Publishers; 2003.Search in Google Scholar

[33] Vaidya PD, Rodrigues AE. Glycerol reforming for hydrogen production: a review. Chem Eng Technol. 2009;32:1463–69.10.1002/ceat.200900120Search in Google Scholar

Received: 2018-06-15
Revised: 2018-08-06
Accepted: 2018-08-08
Published Online: 2018-09-01

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