Abstract
Hydrogen is considered as the main energy genesis of the future. Many applications have been considered for the use of hydrogen as an energy source, especially in the polymer electrolyte membrane fuel cell (PEMFC). Ethanol steam reforming (ESR) is considered to be the most viable technology, because ethanol can be produced from a bio-refinery which can be easily distributed and controlled. The kinetics of ESR have been studied based on different noble metals as well as non-noble metals using supporters in the form of metal oxides, mixed metal oxides, spinel, pervoskite, hydrotalcite, etc. The Eley–Rideal (ER) mechanism and the Langamuir–Hinshelwood–Hougen–Watson (LHHW) mechanism have been used to express the kinetics of ESR. Different catalysts will follow different types of kinetics depending on the reaction path and the kind of model preferred for the development of the kinetics. LHHW mechanism is preferred over the ER mechanism due to its accuracy and the highest activation energy associated with it. This study reviews the generalized mechanistic kinetics for the ESR using fixed bed reactor to produce hydrogen.
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Abbreviations
- AAD:
-
Average absolute deviation
- ER:
-
Eley–Rideal
- ESR:
-
Ethanol steam reforming
- LHHW:
-
Langmuir–Hinshelwood–Hougen–Watson
- RDS:
-
Rate determining step
- WGS:
-
Water gas shift
- \(\Delta H\) :
-
Heat of adsorption
- \(C\) :
-
Concentration of reaction species
- \(C_{\text{T}}\) :
-
Concentration of active sites
- \(E_{\text{a}}\) :
-
Activation energy
- \(F\) :
-
Molar flow rate
- \(k\) :
-
Kinetic rate constant
- \(K\) :
-
Adsorption constant for species or Equilibrium constant of reaction
- \(P\) :
-
Partial pressure of reaction species
- \(R\) :
-
Universal gas constant
- \(r\) :
-
Rate of reaction
- T :
-
Temperature
- W :
-
Weight of the catalyst
- X :
-
Conversion
References
Aboudheir A, Akande A, Idem R, Dalai A (2006) Experimental studies and comprehensive reactor modelling of hydrogen production by the catalytic reforming of crude ethanol in a packed bed tubular reactor over a Ni/Al2O3 catalyst. Int J Hydrog Energy 31:752–761. https://doi.org/10.1016/j.ijhydene.2005.06.020
Akande A, Idem R, Dalai A (2005) Synthesis, characterisation and performance evaluation of Ni/Al2O3 catalysts for reforming of crude ethanol for hydrogen production. Appl Catal A 287:159–175. https://doi.org/10.1016/j.apcata.2005.03.046
Akande A, Aboudheir A, Idem R, Dalai A (2006) Kinetic modelling of hydrogen production by the catalytic reforming of crude ethanol over co-precipitated Ni-Al2O3 catalyst in a packed bed tubular reactor. Int J Hydrog Energy 31:1707–1715. https://doi.org/10.1016/j.ijhydene.2006.01.001
Akpan E, Akande A, Aboudheir A, Ibrahim H, Idem R (2007) Experimental, kinetic and 2-D reactor modelling for simulation of the production of hydrogen by the catalytic reforming of concentrated crude ethanol over a Ni-based commercial catalyst in a packed bed tubular reactor. Chem Eng Sci 62:3112–3126. https://doi.org/10.1016/j.ces.2007.03.006
Aupretre F, Descorme C, Duprez D (2002) Bio-ethanol catalytic steam reforming over supported metal oxide. Catal Commun 3:263–267. https://doi.org/10.1016/S1566-7367(02)00118-8
Aupretre F, Descrome C, Duprez D, Casanave D, Uzio D (2005) Ethanol steam reforming over MgxNi1-xAl2O3 spinel oxide based Rh catalysts. J Catal 233:464–477. https://doi.org/10.1016/j.jcat.2005.05.007
Bshish A, Yaakob Z, Narayanan B, Ramakrishnan R, Ebshish A (2011) Steam reforming of ethanol for hydrogen production. Chem Pap 65(3):251–266. https://doi.org/10.2478/s11696-010-0100-0
Cavallaro S, Chiodo V, Freni S, Mondello N, Frusteri F (2003a) Performance of Rh/Al2O3 catalyst in the steam reforming of ethanol: H2 production for MCFC. Appl Catal A 249:119–128. https://doi.org/10.1016/S0926-860X(03)00189-3
Cavallaro S, Chiodo V, Vita A, Ferni S (2003b) Hydrogen production by auto-thermal reforming of ethanol on Rh/Al2O3 catalyst. J Power Sources 123:10–16. https://doi.org/10.1016/S0378-7753(03)00437-3
Chen CC, Tseng HH, Lin YL, Chen HW (2017) Hydrogen production and carbon dioxide enrichment from ethanol steam reforming followed by water gas shift reaction. J Clean Prod 162:1430–1441. https://doi.org/10.1016/j.jclepro.2017.06.149
Comas J, Marino F, Lamborde M, Amadeo N (2004) Bio-ethanol steam reforming on Ni/Al2O3 catalyst. Chem Eng J 98:61–68. https://doi.org/10.1016/S1385-8947(03)00186-4
Comas J, Dieuzeide L, Baronetti G, Laborde M, Amadeo N (2006) Methane steam reforming and ethanol steam reforming using a Ni(II)–Al(III) catalyst prepared from lamellar double hydroxides. Chem Eng J 118:11–15. https://doi.org/10.1016/j.cej.2006.01.003
Compagnoni M, Tripodi A, Rosseti I (2017) Parametric study and kinetic testing for ethanol steam reforming. Appl Catal B Environ 203:899–909. https://doi.org/10.1016/j.apcatb.2016.11.002
Das D, Veziroglu TN (2001) Hydrogen production by biological processes: a survey of Literature. Int J Hydrog Energy 26:13–28. https://doi.org/10.1016/S0360-3199(00)00058-6
Dehkordi KT, Hormozi F, Jahangiri M (2016) Using conical reactor to improve efficiency of ethanol steam reforming. Int J Hydrog Energy 41:17084–17092. https://doi.org/10.1016/j.ijhydene.2016.07.040
De-Souza M, Zanin GM, Moraes FF (2002) Parametric study of hydrogen production from ethanol steam reforming in a membrane microreactor. Braz J Chem Eng 30(02):355–367. https://doi.org/10.1590/S0104-66322013000200013
Diagne C, Idriss H, Kiennemann A (2008) Hydrogen production by ethanol reforming over Rh/CeO2–ZrO2 catalysts. Catal Commun 3(12):565–571. https://doi.org/10.1016/s1566-7367(02)00226-1
Dobosz J, Malecka M, Zawadzki M (2018) Hydrogen generation via ethanol steam reforming over Co/HAp catalysts. J Energy Inst 91:411–423. https://doi.org/10.1016/j.joei.2017.02.001
Domínguez M, Cristiano G, López E, Llorca J (2011) Ethanol steam reforming over cobalt talc in a plate microreactor. Chem Eng J 176–177:280–285. https://doi.org/10.1016/j.cej.2011.03.087
Dou B, Zhang H, Cui G, Wang Z, Jiang B, Wang K, Chen H, Xu Y (2018) Hydrogen production by sorption-enhanced chemical looping steam reforming of ethanol in an alternating fixed-bed reactor: sorbent to catalyst ratio dependencies. Energy Convers Manag 155:243–252. https://doi.org/10.1016/j.enconman.2017.10.075
Espinal R, Anzola A, Adrover E, Roig M, Chimentao R, Medina F (2014) Durable ethanol steam reforming in a catalytic membrane reactor at moderate temperature over cobalt hydrotalcite. Int J Hydrog Energy 39:10902–10910. https://doi.org/10.1016/j.ijhydene.2014.05.127
Falco MD (2008) Pd-based membrane steam reformers: a simulation study of reactor performance. Int J Hydrog Energy 33:3036–3040. https://doi.org/10.1016/j.ijhydene.2008.03.006
Fatma SB, Aksoylu AE, Osnan I (2008) Steam reforming of ethanol over Pt/Ni Catalyst. Catal Today 138:183–186. https://doi.org/10.1016/j.apcatb.2010.11.030
Fatsikostas AN, Verykios XE (2004) Reaction network of steam reforming of ethanol over Ni-based catalysts. J Catal 225:439–452. https://doi.org/10.1016/j.jcat.2004.04.034
Fierro V, Akdim O, Mirodatos C (2003) On-board hydrogen production in a hybrid electric vehicle by bio-ethanol oxidative steam reforming over Ni and noble metal-based catalysts. Green Chem 5:20–24. https://doi.org/10.1039/b208201m
Froment GF, Bischoff KB (1990) Chemical reactor analysis and design. Wiley Inc., New York
Gallucci F, Falco MD, Tosti S, Marrelli L, Basile A (2008) Ethanol steam reforming in a dense Pd–Ag membrane reactor: a modelling work. Comparison with the traditional system. Int J Hydrog Energy 33:644–651. https://doi.org/10.1016/j.ijhydene.2007.10.039
Galvita VV, Belyaev VD, Semikolenov VA, Tsiakaras P, Frumin A, Sobyanin VA (2002) Ethanol decomposition over Pd-Based Catalyst in the presence of steam. React Kinet Catal Lett 76(2):343–351. https://doi.org/10.1023/a:1016500431269
Garcia EY, Laborde MA (1991) Hydrogen production by the steam reforming of ethanol: thermodynamic analysis. Int J Hydrog Energy 16(5):307–312. https://doi.org/10.1016/0360-3199(91)90166-G
Ghirardi ML, Zhang L, Lee JW, Flynn T, Seibert M, Greenbaum E, Melis A (2000) Microalgae: a green source of renewable H2. Trends Biotechnol 18:506–511. https://doi.org/10.1016/S0167-7799(00)01511-0
Goerke O, Pfeifer P, Schubert P (2004) Water gas shift reaction and selective oxidation of CO in microreactors. Appl Catal A 263(1):11–18. https://doi.org/10.1016/j.apcata.2003.11.036
Graschinsky C, Laborde M, Amadeo N, Valant A (2010) Ethanol steam reforming over Rh (1%) MgAl2O4/Al2O3: a kinetic study. Ind Eng Chem Res 49:12383–12389. https://doi.org/10.1021/ie101284k
Haryanto A, Fernando S, Murali N, Adhikari S (2005) Current status of hydrogen production techniques by steam reforming of ethanol: review. Energy Fuels 19:2098–2106. https://doi.org/10.1021/ef0500538
Hedayati A, Corre LO, Lacamere B, Llorca J (2016) Experimental and exergy evaluation of ethanol catalytic steam reforming in a membrane reactor. Catal Today 268:68–78. https://doi.org/10.1016/j.cattod.2016.01.058
Jordi L, Narcis H, Joaquim S, Pilar R (2002) Efficient production of hydrogen over supported Cobalt catalyst from ethanol steam reforming. J Catal 209:306–317. https://doi.org/10.1006/jcat.2002.3643
Juan-Juan J, Roman-Martinez MC, Illan-Gomez MJ (2004) Catalytic activity and characterization of Ni/Al2O3 and Ni/Al2O3 catalysts for CO2 methane reforming. Appl Catal A 264:169–174. https://doi.org/10.1016/j.apcata.2003.12.040
Kaddouri A, Mazzocchia C (2004) A study of the influence of the synthesis conditions upon the catalytic properties of Co/SiO2 or Co/Al2O3 catalysts used for ethanol steam reforming. Catal Commun 5(6):339–345. https://doi.org/10.1016/j.catcom.2004.03.008
Levin DB, Pitt L, Love M (2004) Biohydrogen production: prospects and limitations to practical application. Int J Hydrog Energy 29:173–185. https://doi.org/10.1016/S0360-3199(03)00094-6
Li T, Zhang J, Xie X, Yin X, An X (2015) Montmorillonite-supported Ni nanoparticles for efficient hydrogen production from ethanol steam reforming. Fuel 143:55–62. https://doi.org/10.1016/j.fuel.2014.11.033
Li L, Tang D, Song Y, Jiang B, Zhang Q (2018) Hydrogen production from ethanol steam reforming on Ni-Ce/MMT catalysts. Energy 149:937–943. https://doi.org/10.1016/j.energy.2018.02.116
Liguras DK, Kondarides DI, Verykios XE (2003) Production of hydrogen for fuel cells by steam reforming of ethanol over supported noble metal catalysts. Appl Catal B 43:345–354. https://doi.org/10.1016/s0926-3373(02)00327-2
Llera I, Mas V, Bergamini ML, Laborde M, Amadeo N (2012) Bio-ethanol steam reforming on Ni based catalyst. Kinetic study. Chem Eng Sci 71:356–366. https://doi.org/10.1016/j.ces.2011.12.018
Llorca J, Homs N, Sales J, Piscina R (2002) Efficient production of hydrogen over supported Cobalt catalyst from steam reforming. J Catal 209:306–317. https://doi.org/10.1006/jcat.2002.3643
Lulianelli A, Dalena F, Basile A (2017) Chapter-7—steam reforming, preferential oxidation and autothermal reforming of ethanol for hydrogen production in membrane reactors. Ethanol. https://doi.org/10.1016/b978-0-12-811458-2.00007-9
Ma R, Castro-Dominguez B, Mardilovich IP, Dixon AG, Ma YH (2016) Experimental and simulation studies of the production of renewable hydrogen through ethanol steam reforming in a large-scale catalytic membrane reactor. Chem Eng J 303:302–313. https://doi.org/10.1016/j.cej.2016.06.021
Ma R, Dominguez-Castro B, Dixon AG, Ma YH (2018) CFD study of heat and mass transfer in ethanol steam reforming in a catalytic membrane reactor. Int J Hydrog Energy 43:7662–7674. https://doi.org/10.1016/j.ijhydene.2017.08.173
Marcelo S, Batista A, Rudya K, Santos A, Elisabete M, Assaf A, José M, Assaf B, Edson A, Ticianelli A (2004) High efficiency steam reforming of ethanol by cobalt-based catalysts. J Power Sources 134:27–32. https://doi.org/10.1016/j.jpowsour.2004.01.052
Marino F, Boveri M, Baronetti G, Laborde M (2004) Hydrogen production via catalytic gasification of ethanol. A mechanism proposal over copper-nickel catalysts. Int J Hydrog Energy 29:67–71. https://doi.org/10.1016/S0360-3199(03)00052-1
Mas V, Kipreos R, Amadeo N, Laborde M (2006) Thermodynamic analysis of ethanol/water system with the stoichiometric method. Int J Hydrog Energy 31:21–28. https://doi.org/10.1016/j.ijhydene.2005.04.004
Mas V, Bergamini ML, Baronetti G, Amadeo N, Laborde M (2008) A kinetic study of ethanol steam reforming using a nickel based catalyst. Top Catal 51:39–48. https://doi.org/10.1007/s11244-008-9123-y
Mathure P, Ganguly S, Patwardhan A, Saha RK (2007) Steam reforming of ethanol using a commercial nickel-based catalyst. Ind Eng Chem Res 46:8471–8479. https://doi.org/10.1021/ie070321k
Montero C, Remiro A, Benito LP, Bibao J, Gayubo AG (2018) Optimum operating conditions in ethanol steam reforming over a Ni/La2O3-αAl2O3 catalyst in a fluidized bed reactor. Fuel Process Tech 169:207–216. https://doi.org/10.1016/j.fuproc.2017.10.003
Morgenstern D, Fornango J (2005) Low-temperature reforming of ethanol over copper-plated Raney nickel: a new route to sustainable hydrogen for transportation. Energy Fuels 19:1708–1716. https://doi.org/10.1021/ef049692t
Peela NR, Kunzru D (2011) Steam reforming of ethanol in a microchannel reactor: kinetic study and reactor simulation. Ind Eng Chem Res 50:12881–12894. https://doi.org/10.1021/ie200084b
Reith JH, Wijffels RH, Barton H (2003) Bio-methane and biohydrogen: status and perspectives of biological methane and hydrogen production. Dutch Biological Hydrogen Foundation, Petten, p 166
Rossetti I, Compagnoni M, Torli M (2015) Process simulation and optimization of H2 production from ethanol steam reforming and its use in fuel cells 1. Thermodynamic and kinetic analysis. Chem Eng J 281:1024–1035. https://doi.org/10.1016/j.cej.2015.08.025
Ruocco C, Meloni E, Palma V, Annaland MS, Spallina V, Gallucci F (2016) Pt–Ni based catalyst for ethanol reforming in a fluidized bed membrane reactor. Int J Hydrog Energy 41:20122–20136. https://doi.org/10.1016/j.ijhydene.2016.08.045
Sahoo DR, Vajpai S, Patel S, Pant KK (2007) Kinetic modelling of steam reforming of ethanol for the production of hydrogen over Co/Al2O3 catalyst. Chem Eng J 125:139–147. https://doi.org/10.1016/j.cej.2006.08.011
Serra M, Ocampo-Martinez C, Li M, Llorca J (2017) Model predictive control for ethanol steam reformers with membrane separation. Int J Hydrog Energy 42:1949–1961. https://doi.org/10.1016/j.ijhydene.2016.10.110
Sheng PY, Bowmaker GA, Idriss H (2004) The reaction of ethanol over Au/CeO2 catalyst. Appl Catal A 261:171–181. https://doi.org/10.1016/j.apcata.2003.10.046
Sun J, Qiu XP, Wu F, Zhu WT (2005) H2 from steam reforming of ethanol at low temperature over Ni/Y2O3, Ni/La2O3 and Ni/Al2O3 catalysts for fuel-cell application. Int J Hydrog Energy 30:437–445. https://doi.org/10.1016/j.ijhydene.2004.11.005
Tabakova T, Boccuzzi F, Manzoli M, Andreeva D (2003) FTIR study of low-temperature water-gas shift reaction on Gold/Ceria catalyst. Appl Catal A 252(2):385–397. https://doi.org/10.1016/S0926-860X(03)00493-9
Tabakova T, Boccuzzi F, Manzoli M, Sobczak JW, Idakiev VV, Andreeva D (2004) Effect of synthesis procedure on the low-temperature WGS activity of Au/Ceria Catalysts. Appl Catal B 49(2):73–81. https://doi.org/10.1016/j.apcatb.2003.11.014
Vaidya PD, Rodrigues AE (2006) Kinetics of steam reforming of ethanol over the Ru/Al2O3 catalyst. Ind Eng Chem Res 45:6614–6618. https://doi.org/10.1021/ie051342m
Vizcaino A, Arena P, Baronetti G, Carrero A, Calles J, Laborde M, Amadeo N (2008) Ethanol steam reforming on Ni/Al2O3 catalysts: effect of Mg addition. Int J Hydrog Energy 33:3489–3492. https://doi.org/10.1016/j.ijhydene.2007.12.012
Wu C, Dupont V, Nahil AM, Dou B, Chen H, William PT (2017) Investigation of Ni/SiO2 catalysts prepared at different conditions for hydrogen production from ethanol steam reforming. J Energy Inst 90:276–284. https://doi.org/10.1016/j.joei.2016.01.002
Zhang Q, Ling Guo, Zheng X, Xing M, Hao Z (2018) Insight into the reaction mechanism of ethanol steam reforming catalysed by Co–Mo6S8. Mol Phys. https://doi.org/10.1080/00268976.2018.1521011
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The authors would like to thank Prof. Santosh Kumar Gupta of our department for his inspiring guidance.
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Punase, K.D., Rao, N. & Vijay, P. A review on mechanistic kinetic models of ethanol steam reforming for hydrogen production using a fixed bed reactor. Chem. Pap. 73, 1027–1042 (2019). https://doi.org/10.1007/s11696-018-00678-6
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DOI: https://doi.org/10.1007/s11696-018-00678-6