In this study, the production of synthesis gases has been purposed under between 250 o C - 700 o C and 1 - 2 bars pressures. The research was conducted over a commercial BASF catalyst and a laboratory prepared catalyst. The catalyst has a content of different substances including basically NiO/Al 2 O 3 and some additionals (Ca, Mg, Cr, Si). The experimental measurements were carried out within a recently developed experimental equipment which can be operated up to 1200 o and 1 to 3 bars pressures. The study was conducted over a commercial BASF catalyst and a laboratory prepared catalyst under different ethanol/water ratios, temperatures, and catalyst loads. Under the condition when ethanol/water ratios were decreased from 1/2 to 1/10, it was observed that hydrogen ratios increased in exit gas composition of the reactor. With increments in catalyst loads from 1 to 5 grammes, hydrogen ratios in exit gas composition gradually increased. Reaction of ethanol-steam reforming started nearly at 300 o C, and when temperature increments continued further up to 700 o C, hydrogen yields in exit gas compositions of the reactor increased significantly to a range of 70% - 80%. In the case of using commercial BASF catalyst, hydrogen ratios in exit gas composition were found slightly higher than laboratory prepared catalyst. According to our observations, life time of laboratory prepared catalyst was found higher than the commercial BASF catalyst. In this study which kinetic measurements were applied, some kinetic parameters of ethanol-steam reaction were calculated. The mean activation energy of ethanol consumptions at 573 o K - 973 o K was found as 26.87 kJ/mol, approximately. All kinetic measurements were analyzed with a first order reaction rate model. In this study, some diffusion limitations existed, however, overall reaction was chemically controlled.
KeywordsEthanol-Steam ReformingPreparation of CatalystsHydrogen ProductionSynthesis GasCoke Formation
Marino, F.J., Cerrella, E.G., Duhalde, S., Jobbagy, M. and Laborde, M.A. (1998) Hydrogen from Steam Reforming of Ethanol, Characterization and Performance of Copper-Nickel Supported Catalysts. International Journal of Hydrogen Energy, 23, 1095-1101. http://dx.doi.org/10.1016/S0360-3199(97)00173-0
Fishtik, I., Alexander, A., Datta, R. and Geana, D. (2000) A Thermodynamics Analysis of Hydrogen Production by Steam Reforming of Ethanol via Response Reactions. International Journal of Hydrogen Energy, 25, 31-45. http://dx.doi.org/10.1016/S0360-3199(99)00004-X
Galvita, V.V., Semin, G.L., Belyaev, V.D., Semikolenov, V.A., Tsiakaras, P. and Sobyanin,V.A. (2001) Synthesis Gas Production by Steam Reforming of Ethanol. Applied Catalysis A: General, 220, 123-127. http://dx.doi.org/10.1016/S0926-860X(01)00708-6
Therdthianwong, A., Sakulkoakiet, T. and Therdthianwong, S. (2001) Hydrogen Production by Catalytic Ethanol Steam Reforming. Science Asia, 27, 193-198. http://dx.doi.org/10.2306/scienceasia1513-1874.2001.27.193
Lindström, B. (2001) Hydrogen Generation by Steam Reforming of Methanol over Copper-Based Catalysts for Fuel Cell Applications. International Journal of Hydrogen Energy, 26, 923-933. http://dx.doi.org/10.1016/S0360-3199(01)00034-9
Klouz, V., Fierro, V., Denton, P., Katz, H., Lisse, J.P., Bouvot-Mauduit, S. and Mirodatos, C. (2002) Ethanol Reforming for Hydrogen Production in a Hybrid Electric Vehicle: Process Optimization. Journal of Power Sources, 105, 26-34. http://dx.doi.org/10.1016/S0378-7753(01)00922-3
Freni, S., Cavallaro, S., Mondello, N., Spadaro, L. and Frusteri, F. (2002) Steam Reforming of Ethanol on Ni/MgO Catalysts: H2 Production for MCFC. Journal of Power Sources, 108, 53-57. http://dx.doi.org/10.1016/S0378-7753(02)00004-6
Joensen, F. and Rostrup-Nielsen, J.R. (2002) Conversion of Hydrocarbons and Alcohols for Fuel Cells. Journal of Power Sources, 105, 195-201. http://dx.doi.org/10.1016/S0378-7753(01)00939-9
Fatsikostas, A.N., Kondarides, D.I. and Verykios, X.E. (2002) Production of Hydrogen for Fuel Cells by Reformation of Biomass-Derived Ethanol. Catalysis Today, 75, 145-155. http://dx.doi.org/10.1016/S0920-5861(02)00057-3
Cavallaro, S., Chiodo,V., Vita, A. and Freni,S. (2003) Hydrogen Production by Auto-Thermal Reforming of Ethanol on Rh/Al2O3 Catalyst. Journal of Power Sources, 123, 10-16. http://dx.doi.org/10.1016/S0378-7753(03)00437-3
Liguras, D.K, Kondarides, D.I. and Verykios, X.E. (2003) Production of Hydrogen for Fuel Cells by Steam Reforming of Ethanol over Supported Noble Metal Catalysts. Applied Catalysis B: Environmental, 43, 345-354. http://dx.doi.org/10.1016/S0926-3373(02)00327-2
Marino, F., Baronetti, G., Jobbagy, M. and Laborde, M. (2003) Cu-Ni-K/r-Al 2 O 3 Supported Catalysts for Ethanol Steam Reforming Formation of Hydrotalcite-Type Compounds as a Result of Metal-Support Interaction. Applied Catalysis A: General, 238, 41-54. http://dx.doi.org/10.1016/S0926-860X(02)00113-8
Cavallaro, S., Chiodo, V., Freni, S., Mondello, N. and Frusteri, F. (2003) Performance of Rh/Al2O3 Catalyst in the Steam Reforming of Ethanol: H2 Production for MCFC. Applied Catalysis A: General, 249, 119-128. http://dx.doi.org/10.1016/S0926-860X(03)00189-3
Comas, J., Marino, F., Laborde, M. and Amadeo, N. (2004) Bio-Ethanol Steam Reforming on Ni/ Al2O3 Catalyst. Chemical Engineering Journal, 98, 61-68. http://dx.doi.org/10.1016/S1385-8947(03)00186-4
Frusteri, F., Freni, S., Chiodo, V., Spadaro, L., Di Blasi, O., Bonura, G. and Cavallaro, S. (2004) Steam Reforming of Bio-Ethanol on Alkali-Doped Ni/MgO Catalysts: Hydrogen Production for MC Fuel Cell. Applied Catalysis A: General, 270, 1-7. http://dx.doi.org/10.1016/j.apcata.2004.03.052
Akande, A.J., Idem, R.O. and Dalai, A.K. (2005) Synthesis, Characterization and Performance Evaluation of Ni/Al2O3 Catalysts for Reforming of Crude Ethanol for Hydrogen Production. Applied Catalysis A: General, 287, 159-175. http://dx.doi.org/10.1016/j.apcata.2005.03.046
Vesselli, E., Comelli, G., Rosei, R., Freni, S., Frusteri, F. and Cavallaro, S. (2005) Ethanol Auto-Thermal Reforming on Rhodium Catalysts and Initial Steps Simulation on Single Crystals under UHV Conditions. Applied Catalysis A: General, 281, 139-147. http://dx.doi.org/10.1016/j.apcata.2004.11.020
Lisboa, J.S., Santos, D.C.R.M., Passos, F.B. and Noronha, F.B. (2005) Influence of the Addition of Promoters to Steam Reforming Catalysts. Catalysis Today, 101, 15-21. http://dx.doi.org/10.1016/j.cattod.2004.12.005
Velu, S., Suzuki, K., Vijayaraj, M., Barman, S. and Gopinath, C.S. (2005) In Situ XPS Investigations of Cu 1-x Ni x ZnAl- Mixed Metal Oxide Catalysts Used in the Oxidative Steam Reforming of Bio-Ethanol. Applied Catalysis B: Environ- mental, 55, 287-299. http://dx.doi.org/10.1016/j.apcatb.2004.09.007
Aupretre, F., Descorme, C., Duprez, D., Casanave, D. and Uzio, D. (2005) Ethanol Steam Reforming over Mg x Ni 1-x Al 2 O 3 Spinel Oxide-Supported Rh Catalysts. Journal of Catalysis, 233, 464-477. http://dx.doi.org/10.1016/j.jcat.2005.05.007
Mattos, L.V. and Noronha, F.B. (2005) The Influence of the Nature of the Metal on the Performance of Cerium Oxide Supported Catalysts in the Partial Oxidation of Ethanol. Journal of Power Source, 152, 50-59. http://dx.doi.org/10.1016/j.jpowsour.2004.12.052
Benito, M., Sanz, J.L., Isabel, R., Padilla, R., Arjona, R. and Daza, L. (2005) Bio-Ethanol Steam Reforming: Insights on the Mechanism for Hydrogen Production. Journal of Power Sources, 151, 11-17. http://dx.doi.org/10.1016/j.jpowsour.2005.02.046
Frusteri, F., Freni, S., Chiodo,V., Donato, S., Bonura, G. and Cavallaro, S. (2006) Steam and Auto-Thermal Reforming of Bio-Ethanol over MgO and CeO2 Ni Supported Catalysts. International Journal of Hydrogen Energy, 31, 2193-2199. http://dx.doi.org/10.1016/j.ijhydene.2006.02.024
Demirbas, M.F. and Balat, M. (2006) Recent Advances on the Production and Utilization Trends of Bio-Fuels: A Global Perspective. Energy Conversion and Management, 47, 2371-2381. http://dx.doi.org/10.1016/j.enconman.2005.11.014
Barroso, M.N., Gomez, M.F., Arrua, L.A. and Abello, M.C. (2006) Hydrogen Production by Ethanol Reforming over NiZnAl Catalysts. Applied Catalysis A: General, 304, 116-123. http://dx.doi.org/10.1016/j.apcata.2006.02.033
Zhang, B., Tang, X., Li, Y., Cai, W., Xu, Y. and Shen, W. (2006) Steam Reforming of Bio-Ethanol for the Production of Hydrogen over Ceria-Supported Co, Ir and Ni Catalysts. Catalysis Communications, 7, 367-372. http://dx.doi.org/10.1016/j.catcom.2005.12.014
Dolgykh, L., Stolyarchuk, I., Deynega, I. and Strizhak, P. (2006) The Use of Industrial Dehydrogenation Catalysts for Hydrogen Production from Bioethanol. International Journal of Hydrogen Energy, 31, 1607-1610. http://dx.doi.org/10.1016/j.ijhydene.2006.06.028
Akande, A., Aboudheir, A., Idem, R. and Dalai, A. (2006) Kinetic Modeling of Hydrogen Production by the Catalytic Reforming of Crude Ethanol over a Co-Precipitated Ni-Al2O3 Catalyst in a Packed Bed Tubular Reactor. International Journal of Hydrogen Energy, 31, 1707-1715. http://dx.doi.org/10.1016/j.ijhydene.2006.01.001
Sanchez-Sanchez, M.C., Navarro, R.M. and Fierro, J.L.G. (2007) Ethanol Steam Reforming over Ni/M x O y -Al 2 O 3 (M = Ce, La, Zr and Mg) Catalysts: Influence of Support on the Hydrogen Production. International Journal of Hydrogen Energy, 32, 1462-1471. http://dx.doi.org/10.1016/j.ijhydene.2006.10.025
Hsiao,W.I., Lin, Y.S., Chen, Y.C. and Lee, C.S. (2007) The Effect of the Morphology of Nanocrystalline CeO 2 on Ethanol Reforming. Chemical Physics Letters, 441, 294-299. http://dx.doi.org/10.1016/j.cplett.2007.05.024
Ni, M., Leung, D.Y.C. and Leung, M.K.H. (2007) A Review on Reforming Bio-Ethanol for Hydrogen Production. International Journal of Hydrogen Energy, 32, 3238-3247. http://dx.doi.org/10.1016/j.ijhydene.2007.04.038
Frusteri, F. and Freni, S. (2007) Bio-Ethanol, a Suitable Fuel to Produce Hydrogen for a Molten Carbonate Fuel Cell. Journal of Power Sources, 173, 200-209. http://dx.doi.org/10.1016/j.jpowsour.2007.04.065
Campos-Skrobat, F.C., Rizzo-Domingues, R.C.P., Fernandes-Machado, N.R.C. and Cantao, M.P. (2008) Novel Zeolite-Supported Rhodium Catalysts for Ethanol Steam Reforming. Journal of Power Sources, 183, 713-716. http://dx.doi.org/10.1016/j.jpowsour.2008.05.066
Biswas, P. and Kunzru, D. (2008) Oxidative Steam Reforming of Ethanol over Ni/CeO2-ZrO2 Catalyst. Chemical Engineering Journal, 136, 41-49. http://dx.doi.org/10.1016/j.cej.2007.03.057
Denis, A., Grzegorczyk, W., Gac, W. and Machocki, A. (2008) Steam Reforming of Ethanol over Ni/Support Catalysts for Generation of Hydrogen for Fuel Cell Applications. Catalysis Today, 137, 453-459. http://dx.doi.org/10.1016/j.cattod.2008.03.006
Zhang, B., Cai, W., Li, Y., Xu, Y. and Shen, W. (2008) Hydrogen Production by Steam Reforming of Ethanol over an Ir/CeO2 Catalyst: Reaction Mechanism and Stability of the Catalyst. International Journal of Hydrogen Energy, 33, 4377-4386. http://dx.doi.org/10.1016/j.ijhydene.2008.05.022
Vizcaino, A.J., Arena, P., Baronetti, G., Carrero, A., Calles, J.A., Laborde, M.A. and Amadeo, N. (2008) Ethanol Steam Reforming on Ni/Al2O3 Catalysts: Effect of Mg Addition. International Journal of Hydrogen Energy, 33, 3489- 3492. http://dx.doi.org/10.1016/j.ijhydene.2007.12.012
Ren-Xuan, Y., Chuang, K.-H. and Ming-Yen, W. (2014) Hydrogen Production through Methanol Steam Reforming: Effect of Synthesis Parameters on Ni-Cu/CaO-SiO2 Catalysts Activity. International Journal of Hydrogen Energy, 39, 19494-19501. http://dx.doi.org/10.1016/j.ijhydene.2014.09.140
Bizkarra, K., Barrio, V.L., Yartu, A., Requies, J., Arias, P.L. and Cambra, J.F. (2015) Hydrogen Production from n- Butanol over Alümina and Modified Alumina Nickel Catalysts. International Journal of Hydrogen Energy, 40, 5272- 5280. http://dx.doi.org/10.1016/j.ijhydene.2015.01.055
Silva, P.P., Ferreira, R.A., Nunes, J.F., Sousa1, J.A., Romanielo, L.L., Noronha, F.B. and Hori, C.E. (2015) Production of Hydrogen from the Steam and Oxidative Reforming LPG: Thermodynamic and Experimental Study. Brazilian Journal of Chemical Engineering, 32, 647-662. http://dx.doi.org/10.1590/0104-6632.20150323s00003441
Osorio-Vargasa, P., Camposb, C.H., Navarroc, R.M., Fierroc, J.L.G. and Patricio Reyesa, P. (2015) Rh/Al2O3-La2O3 Catalysts Promoted with CeO2 for Ethanol Steamreforming Reaction. Journal of Molecular Catalysis A: Chemical, 407, 169-181. http://dx.doi.org/10.1016/j.molcata.2015.06.031
Ayodele, B.V., Khan, M.R. and Cheng, C.K. (2015) Syngas Production from CO2 Reforming of Methane over Ceria Supported Cobalt Catalyst: Effects of Reactants Partial Pressure. Journal of Natural Gas Science and Engineering, 27, 1016-1023. http://dx.doi.org/10.1016/j.jngse.2015.09.049
Marinhoa, A.L., Rabelo-Netob, R.C., Noronhab, F.B. and Mattosa, L.V. (2016) Steam Reforming of Ethanol over Ni-Based Catalysts Obtained from LaNiO 3 and LaNiO 3 /CeSiO 2 Perovskite-Type Oxides for the Production of Hydrogen. Applied Catalysis A: General, 520, 53-64. http://dx.doi.org/10.1016/j.apcata.2016.03.032
Levent, M., Küçük, Ö. and Çalban, T. (2008) Hydrogen Production with Catalytic Coal-Steam Gasification Process. 7th National Clean Energy Symposium(UTES 2008), Istanbul, 17-19 December 2008, 555-563.
Levent, M., Agbaba, M. and Sahin, Y. (2009) Hydrogen Production with Ethanol-Steam Reforming Process in a Fixed Bed Reactor over Commercial BASF Catalyst. 5th International Advanced Technologies Symposium (IATS’09), Karabük University, 13-15 May 2009, 1756-1761.
Agbaba, M., Levent, M. and Sahin, Y. (2009) Hydrogen Production by Propane-Steam Reforming Process in a Fixed Bed Reactor. Nuclear and Renewable Energy Sources with International Participation Symposium, Gazi University, 28-29 September 2009, 1-6.
Agbaba, M., Levent, M. and Sahin,Y. (2014) Production of Synthesis Gases from Catalytic Steam Reforming of Ethanol and Propane Processes. 2014 13th International Conference on Clean Energy (ICCE 2014), Istanbul, 8-12 June 2014, 1312-1321.
Agbaba, M. (2013) Catalytic Hydrogen Production with Ethanol and Propane Steam Reforming Process. PhD Thesis, Graduate School of Natural and Applied Science, Atatürk University, Erzurum.
Fogler, H.S. (1999) Elements of Chemical Reaction Engineering. 3rd Edition, Prentice-Hall Inc., Upper Saddle River.
Guczi, L. and Erdöhelyi, A. (2007) Catalysis for Alternative Energy Generation. Chapter 4, Reforming of Ethanol, Springer, New York, 129-174.
Spivey, J.J. and Dooley, K.M. (2007) Catalysis: Specialist Periodical Reports. Vol. 20, The Royal Society of Chemistry Publishing, MPG Books Ltd., Cambridge, 65-106.
Mathure, P.J., Ganguly, S., Patwardhan, A.V. and Saha, R.K. (2007) Steam Reforming of Ethanol Using a Commercial Nickel-Based Catalyst. Industrial & Engineering Chemistry Research, 46, 8471-8479. http://dx.doi.org/10.1021/ie070321k