Bioenergy systems for the future 9 h2 production from bioalcohols and biomethane steam reforming in membrane reactors

Bioenergy systems for the future 9 h2 production from bioalcohols and biomethane steam reforming in membrane reactors Bioenergy systems for the future 9 h2 production from bioalcohols and biomethane steam reforming in membrane reactors Bioenergy systems for the future 9 h2 production from bioalcohols and biomethane steam reforming in membrane reactors Bioenergy systems for the future 9 h2 production from bioalcohols and biomethane steam reforming in membrane reactors Bioenergy systems for the future 9 h2 production from bioalcohols and biomethane steam reforming in membrane reactors

H2 production from bioalcohols and biomethane steam reforming in membrane reactors A Iulianelli*, F Dalena*, A Basile† *University of Calabria, Rende, Italy, †Institute on Membrane Technology (ITM-CNR), Rende, Italy Abbreviations BH2 BH2 O CR dP Ea JH MR MW n p PEMFC pH2 pH2 Àperm pH2 Àret PSS R T hydrogen permeability preexponential factor conventional reactor pore diameter activation energy hydrogen flux permeating through the membrane membrane reactor molecular weight of diffusing gas dependence factor of the hydrogen flux on the hydrogen partial pressure pressure proton exchange membrane fuel cell hydrogen partial pressure hydrogen partial pressures in the permeate side hydrogen partial pressures in the retentate side porous stainless steel universal gas constant temperature Symbols δ η ΔpH2 ε τ membrane thickness viscosity transmembrane hydrogen partial pressure membrane porosity tortuosity Bioenergy Systems for the Future http://dx.doi.org/10.1016/B978-0-08-101031-0.00009-0 © 2017 Elsevier Ltd All rights reserved 322 9.1 Bioenergy Systems for the Future Introduction The previsions on the hydrogen exploitation in the future indicate that it will play a more consistent role as a fuel for large-scale sustainable energy systems (Fig 9.1) up to substituting the liquid, solids, and methane utilization as well (Dunn, 2002) As indicated by the concepts of the hydrogen economy, hence, hydrogen will represent the main fuel in the next century for an economic sustainable growth (Moriarty and Honnery, 2007) In the meanwhile, conventional techniques used for producing hydrogen need to be strongly revised and redesigned to match the requirements of a sustainable development Therefore, the introduction of alternative systems coupled to the exploitation of renewable sources such as the membrane reactors (MRs) has fostered the production of high-grade hydrogen Furthermore, the International Energy Agency has recently published the technology road map toward hydrogen and fuel cells, pointing out that the world economy is still based on the derived of fossil-fuel utilization and that renewable sources exploitation is strictly required to move on a world hydrogen-based energy system (Van der Hoeven, 2015) Proton exchange membrane fuel cells (PEMFCs) convert efficiently the chemical energy into electricity via indirect reaction of hydrogen and oxygen and, furthermore, are zero-pollutant emission devices (Bose et al., 2011) Low-temperature PEMFCs normally work at temperature lower than 100°C and tolerate up to 10 ppm of CO in the high-grade hydrogen stream supplied, owing to the CO poisoning effect on the anodic Pt-based catalyst Nowadays, Fig 9.1 Prevision about hydrogen utilization in a large-scale sustainable energy system Reproduced with permission from Dunn, S., 2002 Hydrogen futures: toward a sustainable energy system Int J Hydrogen Energy 27, 235-264 H2 production from bioalcohols and biomethane steam reforming in membrane reactors 323 hydrogen is industrially produced by steam reforming of natural gas in conventional reactors (CRs) Hence, the reformed stream coming out from the CR contains besides hydrogen also such by-products as CO, CH4, and CO2 As a consequence, this hydrogen-rich stream needs to be purified before supplying a PEMFC, and conventionally, this takes place via a multistage process (Iulianelli et al., 2012) As an alternative solution to the aforementioned multistage process, the application of the MR technology constitutes an interesting option for intensifying the whole process, by combining the reforming reaction for generating hydrogen and its purification in a single stage (Basile et al., 2016; Lu et al., 2007) Nevertheless, only a few industrial-scale MR applications can be noticed, and one of them is represented by the Tokyo Gas Company Ltd (E-net [1]) More in details, the most significant aspect of a MR is represented by the presence of the membrane in the reaction system, which makes possible to display the thermodynamic equilibrium conversion of the equivalent CR (in an equilibrium-restricted reaction) due to the selective removal of a product from the reaction system (i.e., hydrogen), promoting the so-called shift effect on the reaction itself, which proceeds with a higher product formation and consequent conversion enhancement However, MR technology can be applied in various fields, each of them depending on which kind of process itself has to be performed and, consequently, on which kind of membrane has to be considered as best solution Therefore, the MRs can be classified by taking into account the role of the membranes toward the removal/addition of various chemical species and, referring to their materials or structures, giving particular relevance to the selectivity of the permeation of such products with respect to other ones Hence, it is possible to summarize the different classes of MRs in (1) (2) (3) (4) (5) (6) (7) dense and porous inorganic MRs (Iulianelli et al., 2012; Lu et al., 2007; Lin, 2001), polymeric MRs (Bose et al., 2011; Gu et al., 2016), zeolite MRs (Wang and Yan, 2015), photocatalytic MRs (Mozia, 2010), enzyme MRs (Uragami, 2011), membrane bioreactors (Lebrero et al., 2013; Calabro`, 2013), electrochemical MRs (fuel cells, electrolytic cells, etc.) (Datta et al., 2015; Chatenet et al., 2010) In particular, the purposes of this chapter are related to the MR technology application to biofuel reforming reaction for producing hydrogen, with particular relevance to the application of Pd-based membranes 9.2 Inorganic MRs A real interest toward the application of MR technology was noticed when innovative inorganic membrane materials and development of high-temperature membrane processes took place (Basile et al., 2013; Menendez, 2011) Industrially, various heterogeneous gas-solid catalytic processes, conventionally carried out in fixed-, fluidized-, or trickle-bed reactors, are mostly performed at high temperatures and 324 Bioenergy Systems for the Future in chemically harsh ambient Consequently, inorganic membranes are favored material with respect to the polymeric ones for their utilization in MRs It is well recognized that the separation behavior of an inorganic membrane housed in an MR gives several benefits to enhance the performance of a catalytic system Here, we present the advantages due to the utilization of inorganic MRs to integrate a chemical reaction involving a biosource as a reactant (e.g., ethanol, methanol, glycerol, biogas, and acetic acid) with a membrane process (i.e., H2 separation) Thus, by taking into account the crucial role of the inorganic membrane, it is useful to subdivide them as generically resumed below: l l l l Macroporous membranes, with a pore size >50 nm Mesoporous membranes, with a pore size between and 50 nm Microporous membranes, with smaller pore size of nm Dense membranes, with pore size 90 % 38 % 100 Unsupported Pd-Ru-In Unsupported Pd-Cu Singh et al., 2014 MateosPedrero et al., 2015 Liguori et al., 2014 Israni and Harold, 2011 Rei et al., 2011 Lin and Rei, 2001 Basile et al., 2006 Lytkina et al., 2016 Iulianelli et al., 2008 Itoh et al., 2002 Wieland et al., 2002 Bioenergy Systems for the Future Supported Pd-Ag on α-Al2O3 Supported Pd on α-Al2O3 Reference SiO2/γ-Al2O3/PtSiO2/PSS Carbon molecular sieve Carbon supported Carbon supported a 330°C Cu/ZnO/ Al2O3 Cu-Zn/ based Cu-Zn/ based CuO/ZnO/ Al2O3 CuO/ Al2O3/ ZnOMgO Cu/ZnO/ Al2O3 50 3/1 280 2.5 91 46 % 100 – 3/1 260 – 42 98 – 1.3/1 230 – 100 9,1 – – 4/1 200 % 95 % 84 – – 3/1 250 55 – % 80 Bricen˜o et al., 2012 – 1.5/1 250 % 99 – 97 Zhang et al., 2006 Ghasemzadeh et al., 2013 Lee et al., 2008 Lee et al., 2006 Sà et al., 2011 H2 production from bioalcohols and biomethane steam reforming in membrane reactors Unsupported Pd-Ag SiO2/γ-Al2O3 335 336 Bioenergy Systems for the Future while Iulianelli et al (2008) and Ghasemzadeh et al (2013) adopted a thinner Pd-Ag (50 μm of thickness) unsupported membrane in tubular shape, and Wieland et al (2002) utilized a Pd-Cu unsupported membrane with a wall thickness of 25 μm In all the aforementioned cases, around 100% of hydrogen purity was reached during MSR reaction for temperatures ranging between 200°C and 300°C However, for both supported and unsupported Pd-based MRs reported in Table 9.2, it was demonstrated that the MRs show greater performance than the equivalent CRs in terms of methanol conversion, with the further advantage of recovering high-grade hydrogen in the permeate stream Table 9.2 also reports some option in the utilization of Pd-based membranes in MRs For example, Lee et al (2006, 2008) performed MSR reaction in supported SiO2/γ-Al2O3/Pt-SiO2/PSS and SiO2/γ-Al2O3 MRs, achieving 100% of methanol conversion by using the SiO2/γ-Al2O3/Pt-SiO2/PSS membrane, although the hydrogen recovery was quite low (80% Bricen˜o et al (2012) prepared a carbon-based membrane supported on a porous ceramic support of TiO2 coated with ZrO2, to be housed in an MR for carrying out MSR reaction, obtaining more than 50% of methanol conversion with a recovered stream having a hydrogen permeate purity of around 80% Really interesting results were obtained by Zhang et al (2006), who studied MSR reaction in an MR housing a tubular carbon membrane with an ID of mm and a wall thickness of 20–30 μm and sealed inside a stainless steel tube Around 100% of methanol conversion was obtained in the temperature range of 200°C–250°C, with a hydrogen permeate purity around 97% 9.3.3 Bio-gas steam reforming Currently, most of the worldwide demand for hydrogen comes from natural gas, which can be processed in conventional reformers via steam reforming, partial oxidation, and autothermal reforming reactions In particular, $50% of the global hydrogen demand is satisfied by natural gas steam reforming reaction, which represents the most common process for generating hydrogen, although its impact on the climate is quite negative due to the collateral emissions of greenhouse gases The entire conventional process to transform natural gas into hydrogen involves a conventional reformer, water-gas shift (WGS) reactors (high-temperature and low-temperature WGS reactors), and successive stages for the hydrogen separation and purification such as pressure swing adsorption and preferential oxidation reactors (Fig 9.4) In the viewpoint of process intensification strategy, numerous studies in this field evaluated the benefits in using alternative solutions to the conventional processes such as the MRs for producing and simultaneously purifying hydrogen in only one stage (Iulianelli et al., 2016a,b) H2 production from bioalcohols and biomethane steam reforming in membrane reactors LT-WGS reactor H2, CO, CO2, not Conventional reacted CH4 and steam reformer T = 800°C–1000°C HT-WGS reactor WGS stages Natural gas + Steam 337 PrOx reactor PSA Other Fig 9.4 Conventional multistage process for natural gas steam reforming and hydrogen separation/purification More recently, the need of coupling green processes and bio-derived sources is strongly emerged, and a growing attention has been paid toward the hydrogen generation from biogas (Brunetti et al., 2015; Bollini et al., 2013) As a versatile raw feedstock, biogas can represent an alternative to natural gas exploitation, thereby reducing the greenhouse gas emissions Its composition depends on the typology of residual biomass (among animal waste, sewage treatment plants, or industrial wastewater) used during the anaerobic digestion process Nevertheless, biogas is mainly constituted by methane and carbon dioxide, besides traces of H2S, NH3, hydrogen, nitrogen, oxygen, and steam Regarding the combination of biogas reforming with MR technology, at the moment, only a few works are noticeable, and Table 9.3 reports the performance of a restricted number of applications in this field As shown in Table 9.3, only Iulianelli et al (2015) adopted a supported Pd/Al2O3 membrane (7 μm of palladium layer) in the MR for carrying out the biogas steam reforming reaction, obtaining at relatively low temperature and pressure (450°C and 3.5 bar) a methane conversion around 30% with a correspondent hydrogen recovery of 70% and 96% in concentration In the other cases, really thick unsupported Pd or Pd-Ag dense wall membranes were used, favoring a recovery of a high-grade hydrogen stream (nearly to 100% in purity) with interesting conversions close to 90% as observed by Raybold and Huff (2002) but achieved at high temperature (700°C) The restant recent literature in this field is more concentrated on biogas steam reforming in CRs (Araki et al., 2010; Okubo et al., 2010; Izquierdo et al., 2012, 2014; Galvagno et al., 2013; da Silva et al., 2012; Appari et al., 2014; Saha et al., 2014; Lin et al., 2012; Xu et al., 2010; Damyanova et al., 2011; Lucredio et al., 2012) and, concerning the MRs area, on methane/natural gas steam reforming reaction (Basile et al., 2011a; Iulianelli et al., 2010b; Dittmar et al., 2013; Ligthart et al., 2011; Saric et al., 2012; Hwang et al., 2012; Anzelmo et al., 2016) 9.4 Conclusions This chapter dealt with the production of hydrogen from reforming processes of bioalcohols and biogas to constitute a combination within the renewable sources and green fuel processors as the MRs This combination could drive to an enhancement of the hydrogen generation devices, preserving the ambient from the negative effect due to the derived of fossil-fuel exploitation Therefore, it is expected that 338 Table 9.3 Experimental data from literature about biogas reforming reactions in MRs Membrane typology in MR Supported Pd on α-Al2O3 Unsupported Pd Unsupported Pd-Ag Unsupported Pd-Ag Catalyst Palladium layer (μm) T (°C) p (bar) Conversion (%) H2 recovery (%) H2 purity (%) Ni/Al2O3 450 3.5 30 70 96 Pt/γ-Al2O3 50 650 – 88 – % 100 Ru/Al2O3 200 450 – – % 100 Ru/Al2O3 200 450 – 50 % 100 Reference Iulianelli et al., 2015 Raybold and Huff, 2002 Sato et al., 2010 Va´squez Castillo et al., 2015 Bioenergy Systems for the Future H2 production from bioalcohols and biomethane steam reforming in membrane reactors 339 the utilization of renewable alcohols, such as methanol and ethanol, or biogas could have a higher green impact on both future stationary and portable applications Nevertheless, Pd-based MR technology still presents some issues and challenges to be considered prior to its implementation at industrial scale For sure, in the future, the preparation of composite membranes based on very thin Pd layer, presenting high hydrogen permselectivity and stability under long-term operation, will constitute a possibility of applying realistically the principles of the process intensification strategy, substituting the conventional processes References Adhikari, S., Fernand, S., 2006 Hydrogen membrane separation techniques Ind Eng Chem Res 45, 875–881 Al-Mufachi, N.A., Rees, N.V., Steinberger-Wilkens, R., 2015 Hydrogen selective membranes: a review of palladium-based dense metal membranes Renew Sust Energy Rev 47, 540–551 Anzelmo, B., Wilcox, J., Liguori, S., 2016 Natural gas steam reforming reaction at low temperature and pressure conditions for hydrogen production via Pd/PSS membrane reactor J Membr Sci 522, 343–350 Appari, S., Janardhanan, V.M., Bauri, R., Jayanti, S., Deutschmann, O., 2014 A detailed kinetic model for biogas steam reforming on Ni and catalyst deactivation due to sulfur poisoning Appl Catal A Gen 471, 118–125 Araki, S., Hino, N., Mori, T., Hikazudani, S., 2010 Autothermal reforming of biogas over a monolithic catalyst J Nat Gas Chem 19, 477–481 Basile, A., 2008 Hydrogen production using Pd-based membrane reactors for fuel cells Top Catal 51, 107–122 Basile, A., Tosti, S., Capannelli, G., Vitulli, G., Iulianelli, A., Gallucci, F., Drioli, E., 2006 Cocurrent and counter-current modes for methanol steam reforming membrane reactor: experimental study Catal Tod 118, 237–245 Basile, A., Gallucci, F., Iulianelli, A., De Falco, M., Liguori, S., 2008a Hydrogen production by ethanol steam reforming: experimental study of a Pd-Ag membrane reactor and traditional reactor behaviour Int J Chem Reactor Eng 6, A30 Basile, A., Gallucci, F., Iulianelli, A., Tosti, S., 2008b CO-free hydrogen production by ethanol steam reforming in a Pd-Ag membrane reactor Fuel Cells 1, 62–68 Basile, A., Campanari, S., Manzolini, G., Iulianelli, A., Longo, T., Liguori, S., De Falco, M., Piemonte, V., 2011a Methane steam reforming in a Pd-Ag membrane reformer: an experimental study on the reaction pressure influence at middle temperature Int J Hydrogen Energy 36, 1531–1539 Basile, A., Iulianelli, A., Longo, T., Liguori, S., De Falco, M., 2011b Pd-based selective membrane state-of-the-art In: Marrelli, L., De Falco, M., Iaquaniello, G (Eds.), Membrane Reactors for Hydrogen Production Processes Springer, London, Dordrecht, Heidelberg, New York ISBN: 978-0-85729-150-9, pp 21–55 (Chapter 2) http://dx.doi.org/ 10.1007/978-0-85729-151-6 Basile, A., Pinacci, P., Iulianelli, A., Broglia, M., Drago, F., Liguori, S., Longo, T., Calabro`, V., 2011c Ethanol steam reforming reaction in a porous stainless steel supported palladium membrane reactor Int J Hydrogen Energy 36, 2029–2037 Basile, A., Tong, J., Millet, P., 2013 Inorganic membrane reactors for hydrogen production: an overview with particular emphasis on dense metallic membrane materials In: Handbook 340 Bioenergy Systems for the Future of Membrane Reactors Fundamental Materials Science, Design and Optimisation Woodhead Publishing Series in Energy, vol ISBN: 978-0-85709-414-8, pp 42–148 Basile, A., Iulianelli, A., Liguori, S., 2016 Membrane reactor: an integrated “membrane + reaction” system In: Basile, A., Charcosset, C (Eds.), Integrated Membrane Systems and Processes John Wiley & Sons Ltd, Chichester, ISBN: 978-1-118-73908-2, pp 231–253 http://dx.doi.org/10.1002/9781118739167 Bollini Braga, L., Silveira, J.L., da Silva, M.E., Tuna, C.E., Machin, E.B., Pedroso, D.T., 2013 Hydrogen production by biogas steam reforming: a technical, economic and ecological analysis Renew Sust Energy Rev 28, 166–173 Bose, S., Kuila, T., Nguyen, T.X.H., 2011 Polymer membranes for high temperature proton exchange membrane fuel cell: recent advances and challenges Prog Polym Sci 36, 813–843 Bricen˜o, K., Iulianelli, A., Montane`, D., Garcia-Valls, R., Basile, A., 2012 Carbon molecular sieve membranes supported on non-modified ceramic tubes for hydrogen separation in membrane reactors Int J Hydrogen Energy 37, 13536–13544 Brunetti, A., Sun, Y., Caravella, A., Drioli, E., Barbieri, G., 2015 Process intensification for greenhouse gas separation from biogas: more efficient process schemes based on membrane-integrated systems Int J Greenh Gas Control 35, 18–29 Calabro`, V., 2013 Engineering aspects of membrane bioreactors In: Basile, A (Ed.), Handbook of Membrane Reactors Reactor Types and Industrial Applications Woodhead Publishing Series in Energy, vol Woodhead Publishing, Cambridge, ISBN: 978-0-85709-415-5, pp 3–53 Chatenet, M., Dubau, L., Job, N., Maillard, F., 2010 The (electro)catalyst membrane interface in the proton exchange membrane fuel cell: similarities and differences with nonelectrochemical catalytic membrane reactors Catal Tod 156, 76–86 da Silva, A.L., Dick, L.F.P., M€uller, I.L., 2012 Performance of a PEMFC system integrated with a biogas chemical looping reforming processor: a theoretical analysis and comparison with other fuel processors (steam reforming, partial oxidation and auto-thermal reforming) Int J Hydrogen Energy 37, 6580–6600 Damyanova, S., Pawelec, B., Arishtirova, K., Fierro, J.L.G., 2011 Biogas reforming over bimetallic PdNi catalysts supported on phosphorus-modified alumina Int J Hydrogen Energy 36, 10635–10647 Datta, R., Martino, D.J., Yen, P.-S., 2015 Electrocatalytic membrane reactors (eCMRs) for fuel cell and other applications In: Basile, A., Di Paola, L., Hai, F., Piemonte, V (Eds.), Membrane Reactors for Energy Applications and Basic Chemical Production Woodhead Publishing Series in Energy Woodhead Publishing, Cambridge, ISBN: 978-1-78242223-5, pp 439–487 Dittmar, B., Behrens, A., Schodel, N., Ruttinger, M., Franco, Th., Straczewski, G., Dittmeyer, R., 2013 Methane steam reforming operation and thermal stability of new porous metal supported tubular palladium composite membranes Int J Hydrogen Energy 38, 8759–8771 Dolan, M.D., Dave, N.C., Ilyushechkin, A.Y., Morpeth, L.D., McLennan, K.G., 2006 Composition and operation of hydrogen-selective amorphous alloy membranes J Membrane Sci 285, 30–55 Dunn, S., 2002 Hydrogen futures: toward a sustainable energy system Int J Hydrogen Energy 27, 235–264 E-net [1]: http://www.tokyo-gas.co.jp/index_e.html Espinal, R., Anzola, A., Adrover, E., Roig, M., Chimentao, R., Medina, F., Lo´pez, E., Borio, D., Llorca, J., 2014 Durable ethanol steam reforming in a catalytic membrane reactor at moderate temperature over cobalt hydrotalcite Int J Hydrogen Energy 39, 10902–10910 H2 production from bioalcohols and biomethane steam reforming in membrane reactors 341 Galvagno, A., Chiodo, V., Urbani, F., Freni, F., 2013 Biogas as hydrogen source for fuel cell applications Int J Hydrogen Energy 38, 3913–3920 Ghasemzadeh, K., Liguori, S., Morrone, P., Iulianelli, A., Piemonte, V., Babaluo, A.A., Basile, A., 2013 H2 production by low pressure methanol steam reforming in a dense Pd-Ag membrane reactor in co-current flow configuration: experimental and modeling analysis Int J Hydrogen Energy 36, 16685–16697 Gu, Y., Remigy, J.C., Favier, I., Montserrat, G., Richard, D.N., Lahitte, J.-F., 2016 Membrane reactor based on hybrid nanomaterials for process intensification of catalytic hydrogenation reaction: an example of reduction of the environmental footprint of chemical synthesis from a batch to a continuous flow chemistry process Chem Eng Trans 47, 367–372 Hwang, K.-R., Lee, C.-B., Ryi, S.-K., Lee, S.-W., Park, J.-S., 2012 A multi-membrane reformer for the direct production of hydrogen via a steam-reforming reaction of methane Int J Hydrogen Energy 37, 6601–6607 Israni, S., Harold, M.P., 2011 Methanol steam reforming in single-fiber bed Pd-Ag membrane reactor: experiments and modeling J Membrane Sci 369, 375–387 Itoh, N., 2012 Analysis of equilibrium-limited dehydrogenation and steam reforming in palladium membrane reactors J Jpn Petrol Inst 55, 160–170 Itoh, N., Kaneko, Y., Igarashi, A., 2002 Efficient hydrogen production via methanol steam reforming by preventing back-permeation of hydrogen in a palladium membrane reactor Ind Eng Chem Res 41, 4702–4706 Iulianelli, A., Basile, A., 2010 An experimental study on bio-ethanol steam reforming in a catalytic membrane reactor Part I: temperature and sweep-gas flow configuration Int J Hydrogen Energy 35, 3170–3177 Iulianelli, A., Basile, A., 2011 Hydrogen production from ethanol via inorganic membrane reactors technology: a review Catal Sci Technol 1, 366–379 Iulianelli, A., Longo, T., Basile, A., 2008 Methanol steam reforming in a dense Pd-Ag membrane reactor: The pressure and WHSV effects on CO-free H2 production J Membrane Sci 323, 235–240 Iulianelli, A., Longo, T., Liguori, S., Seelam, P.K., Keiski, R.L., Basile, A., 2009 Oxidative steam reforming of ethanol over Ru-Al2O3 catalyst in a dense Pd-Ag membrane reactor to produce hydrogen for PEM fuel cells Int J Hydrogen Energy 34, 8558–8568 Iulianelli, A., Liguori, S., Longo, T., Tosti, S., Pinacci, P., Basile, A., 2010a An experimental study on bio-ethanol steam reforming in a catalytic membrane reactor Part II: reaction pressure, sweep factor and WHSV effects Int J Hydrogen Energy 35, 3159–3164 Iulianelli, A., Manzolini, G., De Falco, M., Campanari, S., Longo, T., Liguori, S., Basile, A., 2010b H2 production by low pressure methane steam reforming in a Pd-Ag membrane reactor over a Ni-based catalyst: experimental and modeling Int J Hydrogen Energy 35, 11514–11524 Iulianelli, A., Liguori, S., Longo, T., Basile, A., 2012 Inorganic membrane and membrane reactor technologies for hydrogen production In: Honnery, D.R., Moriarty, P (Eds.), Hydrogen Production: Prospects and Processes Energy Science, Engineering and Technology, Nova Science Publishers, Victoria, Australia, ISBN: 978-1-62100-246-8, pp 377–398 (chapter 12) Iulianelli, A., Ribeirinha, P., Mendes, A., Basile, A., 2014 Methanol steam reforming for hydrogen generation via membrane reactors: a review Renew Sust Energy Rev 29, 355–368 Iulianelli, A., Liguori, S., Huang, Y., Basile, A., 2015 Model biogas steam reforming in a thin Pd-supported membrane reactor to generate clean hydrogen for fuel cells J Power Sou 273, 25–32 342 Bioenergy Systems for the Future Iulianelli, A., Liguori, S., Vita, A., Italiano, C., Fabiano, C., Huang, Y., Basile, A., 2016a The oncoming energy vector: hydrogen produced in Pd-composite membrane reactor via bioethanol reforming over Ni/CeO2 catalyst Catal Tod 259, 368–375 Iulianelli, A., Liguori, S., Wilcox, J., Basile, A., 2016b Advances on methane steam reforming to produce hydrogen through membrane reactors technology: a review Catal Rev Sci Eng 58, 1–35 Izquierdo, U., Barrio, V.L., Lago, N., Requies, J., Cambra, J.F., G€ uemez, M.B., Arias, P.L., 2012 Biogas steam and oxidative reforming processes for synthesis gas and hydrogen production in conventional and microreactor reaction systems Int J Hydrogen Energy 37, 13829–13842 Izquierdo, U., Barrio, V.L., Bizkarra, K., Gutierrez, A.M., Arraibi, J.R., Gartzia, L., Ban˜uelos, J., Lopez-Arbeloa, I., Cambra, J.F., 2014 Ni and Rh single bond Ni catalysts supported on Zeolites L for hydrogen and syngas production by biogas reforming processes Chem Eng J 238, 178–188 Lebrero, R., Mun˜oz, R., Kumar, A., Van Langenhove, H., 2013 Membrane bioreactors In: Kennes, C., Veiga, M.C (Eds.), Air Pollution Prevention and Control: Bioreactors and Bioenergy John Wiley & Sons, Ltd, Chichester, pp 155–183 (chapter 7) http://dx.doi org/10.1002/9781118523360 Lee, D.W., Nam, S.E., Sea, B., Ihm, S.K., Lee, K.H., 2006 Preparation of Pt-loaded hydrogen selective membranes for methanol reforming Catal Tod 118, 198–204 Lee, D.W., Park, S.J., Yu, C.Y., Ihm, S.K., Lee, K.H., 2008 Study on methanol reforminginorganic membrane reactors combined with water-gas shift reaction and relationship between membrane performance and methanol conversion J Membrane Sci 316, 63–72 Li, H., Caravella, A., Xu, H.Y., 2016 Recent progress in Pd-based composite membranes J Mater Chem A (37), 14069–14094 Ligthart, D.A.J.M., Pieterse, J.A.Z., Hensen, E.J.M., 2011 The role of promoters for Ni catalysts in low temperature (membrane) steam methane reforming Appl Catal A Gen 405, 108–119 Liguori, S., Iulianelli, A., Dalena, F., Piemonte, V., Huang, Y., Basile, A., 2014 Methanol steam reforming in an Al2O3 supported thin Pd-layer membrane reactor over Cu/ZnO/Al2O3 catalyst Int J Hydrogen Energy 39, 18702–18710 Lim, H., Gu, Y., Oyama, S.T., 2010 Reaction of primary and secondary products in a membrane reactor: Studies of ethanol steam reforming with a silica-alumina composite membrane J Membrane Sci 351, 149–159 Lin, Y.S., 2001 Microporous and dense inorganic membranes: current status and prospective Sep Purif Technol 25, 39–55 Lin, Y.M., Rei, M.H., 2001 Study on hydrogen production from methanol steam reforming in supported palladium membrane reactor Catal Tod 67, 77–84 Lin, W.H., Hsiao, C.S., Chang, H.-F., 2008 Effect of oxygen addition on the hydrogen production from ethanol steam reforming in a Pd-Ag membrane reactor J Membrane Sci 322, 360–367 Lin, W.-H., Liu, Y.-C., Chang, H.-F., 2010 Autothermal reforming of ethanol in a Pd-Ag/Ni composite membrane reactor Int J Hydrogen Energy 35, 12961–12969 Lin, K.-H., Chang, H.-F., Chang, A.C.-C., 2012 Biogas reforming for hydrogen production over mesoporous Ni2xCe1ÀxO2 catalysts Int J Hydrogen Energy 37, 15696–15703 Lu, G.Q., Diniz de Costa, J.C., Duke, M., Giessler, S., Socolow, R., Williams, R.H., Kreutz, T., 2007 Inorganic membranes for hydrogen production and purification: A critical review and perspective J Coll Interface Sci 314, 589–603 Lucredio, A.F., Assaf, J.M., Assaf, E.M., 2012 Reforming of a model biogas on Ni and Rh–Ni catalysts: effect of adding La Fuel Proc Techn 102, 124–131 Lytkina, A.A., Orekhova, N.V., Ermilova, M.M., Belenov, S.V., Guterman, V.E., Efimov, M.N., Yaroslavtsev, A.B., 2016 Bimetallic carbon nanocatalysts for methanol steam reforming in conventional and membrane reactors Catal Tod 268, 60–67 H2 production from bioalcohols and biomethane steam reforming in membrane reactors 343 Ma, R., Castro-Dominguez, B., Mardilovich, I.P., Dixon, A.G., Ma, Y.H., 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 Mallada, R., Menendez, M., 2008 Inorganic Membranes: Synthesis, Characterization and Applications Technology & Engineering, Oxford, p 460 Mateos-Pedrero, C., Silva, H., Pacheco Tanaka, D.A., Liguori, S., Iulianelli, A., Basile, A., Mendes, A., 2015 CuO/ZnO catalysts for methanol steam reforming: the role of the support polarity ratio and surface area Appl Catal B: Env 174, 67–76 Meenendez, M., 2011 Inorganic membrane reactors for energy applications In: Rios, G., Centi, G., Kanellopoulos, N (Eds.), Nanoporous Materials for Energy and the Environment Pan Stanford Publishing Pte Ltd, Gloucester, ISBN: 978-981426717-5, pp 283–297 Menendez, M., 2011 Inorganic membrane reactors for energy application, Source of the Document Nanoporous Materials for Energy and the Environment, pp 283-297 Moriarty, P., Honnery, D., 2007 Intermittent renewable energy: the only future source of hydrogen? Int J Hydrogen Energy 32, 1616–1624 Mozia, S., 2010 Photocatalytic membrane reactors (PMRs) in water and wastewater treatment A review Sep Purif Techn 73, 71–91 Murmura, M.A., Patrascu, M., Annesini, M.C., Palma, V., Ruocco, C., Sheintuch, M., 2015 Directing selectivity of ethanol steam reforming in membrane reactors Int J Hydrogen Energy 40, 5837–5848 Okubo, T., Hideschima, Y., Shudo, Y., 2010 Estimation of hydrogen output from a full-scale plant for production of hydrogen from biogas Int J Hydrogen Energy 35, 13021–13027 Papadias, D.D., Lee, S.H.D., Ferrandon, M., Ahmed, S., 2010 An analytical and experimental investigation of high-pressure catalytic steam reforming of ethanol in a hydrogen selective membrane reactor Int J Hydrogen Energy 35, 2004–2017 Raybold, T.M., Huff, M.C., 2002 Analyzing enhancement of CO2 reforming of CH4 in Pd membrane reactors Aiche J 48, 1051–1061 Rei, M.H., Yeh, G.T., Tsai, Y.H., Kao, Y.L., Shiau, L.D., 2011 Catalysis-spillover-membrane III: the effect of hydrogen spillover on the palladium membrane reactor in the steam reforming reactions J Membrane Sci 369, 299–307 Sà, S., Sousa, J.M., Mendes, A., 2010 Methanol steam reforming in a dual-bed membrane reactor for producing PEMFC grade hydrogen Catal Tod 156, 254–260 Sà, S., Sousa, J.M., Mendes, A., 2011 Steam reforming of methanol over a CuO/ZnO/Al2O3 catalyst part II: a carbon membrane reactor Chem Eng Sci 66, 5523–5530 Saha, B., Khan, A., Ibrahim, H., Idem, R., 2014 Evaluating the performance of non-precious metal based catalysts for sulfur-tolerance during the dry reforming of biogas Fuel 120, 202–217 Saric, M., van Delft, Y.C., Sumbharaju, R., Meyer, D.F., de Groot, A., 2012 Steam reforming of methane in a bench-scale membrane reactor at realistic working conditions Catal Tod 193, 74–80 Sato, T., Suzuki, T., Aketa, M., Ishiyama, Y., Mimura, K., Itoh, N., 2010 Steam reforming of biogas mixtures with a palladium membrane reactor system Chem Eng Sci 65, 451–457 Seelam, P.K., Liguori, S., Iulianelli, A., Pinacci, P., Drago, F., Calabro`, V., Huuhtanen, M., Keiski, R., Piemonte, V., Tosti, S., De Falco, M., Basile, A., 2012 Hydrogen production from bio-ethanol steam reforming reaction in a Pd/PSS membrane reactor Catal Tod 193, 42–48 Singh, A.P., Singh, S., Ganguly, S., Patwardhan, A.V., 2014 Steam reforming of methane and methanol in simulated macro & micro-scale membrane reactors: Selective separation of hydrogen for optimum conversion J Nat Gas Sci Eng 18, 286–295 344 Bioenergy Systems for the Future Uragami, T., 2011 Enzyme-immobilised polymer membranes for chemical reactions In: Basile, A., Gallucci, F (Eds.), Membranes for Membrane Reactors: Preparation, Optimization and Selection John Wiley & Sons, Ltd, Chichester, pp 569–589 (chapter 26) http://dx.doi.org/10.1002/9780470977569 Van der Hoeven, M., 2015 Technology roadmap: hydrogen and fuel cells International Energy Agency, (http://www.iea.org/ November 2016) Va´squez Castillo, J.M., Sato, T., Itoh, N., 2015 Effect of temperature and pressure on hydrogen production from steam reforming of biogas with Pd–Ag membrane reactor Int J Hydrogen Energy 40, 3582–3591 Wang, Z., Yan, Y., 2015 Zeolite thin films and membranes: from fundamental to applications In: Xiao, F.S., Meng, X (Eds.), Zeolites in Sustainable Chemistry: Synthesis, Characterization and Catalytic Applications.In: Part of the series Green Chemistry and Sustainable Technology, ISBN: 978-3-662-47395-5, pp 435–472 Wieland, S., Melin, T., Lamm, A., 2002 Membrane reactors for hydrogen production Chem Eng Sci 57, 1571–1576 Xu, J., Zhou, W., Li, Z., Wang, J., Ma, J., 2010 Biogas reforming for hydrogen production over a Ni–Co bimetallic catalyst: effect of operating conditions Int J Hydrogen Energy 35, 13013–13020 Yan, Y.-F., Zhang, L., Li, L.-X., Tang, Q.Y.M., 2011 Progress in catalytic membrane reactors for high purity hydrogen production J Inorg Mat 26, 1233–1243 Yu, C.Y., Lee, D.W., Park, S.J., Lee, K.Y., Lee, K.H., 2009 Study on catalytic membrane reactor for hydrogen production from ethanol steam reforming Int J Hydrogen Energy 34, 2947–2954 Yun, S., Oyama, S.T., 2011 Correlations in palladium membranes for hydrogen separation: a review J Membrane Sci 375, 28–45 Yun, S., Lim, H., Oyama, S.T., 2012 Experimental and kinetic studies of the ethanol steam reforming reaction equipped with ultrathin Pd and Pd–Cu membranes for improved conversion and hydrogen yield J Membrane Sci 409–410, 222–231 Zhang, X., Hu, H., Zhu, Y., Zhu, S., 2006 Methanol steam reforming to hydrogen in a carbon membrane reactor system Ind Eng Chem Res 45, 7997–8001 Zornoza, B., Casado, C., Navajas, A., 2015 Advances in hydrogen separation and purification with membrane technology In: Doukelis, A., Panopoulos, K., Koumanakos, A., Kakaras, E (Eds.), Palladium Membrane Technology for Hydrogen Production, Carbon Capture and Other Applications: Principles, Energy Production and Other Applications Woodhead Publishing Series in Energy, ISBN: 978-1-78242-234-1, pp 167–191 Further Reading Algieri, C., Comite, A., Capannelli, G., 2013 Zeolite membrane reactors In: Basile, A (Ed.), Handbook of Membrane Reactors Fundamental Materials Science, Design and Optimisation In: Woodhead Publishing Series in Energy, vol Woodhead Publishing, Cambridge, ISBN: 978-0-85709-414-8, pp 245–270 Silva, F.S.A., Benachour, M., Abreu, C.A.M., 2015 Evaluating hydrogen production in biogas reforming in a membrane reactor Braz J Chem Eng 32, 201–210  ... H2 production from bioalcohols and biomethane steam reforming in membrane reactors 9. 3 3 29 Hydrogen production in MRs from bio-alcohols reforming 9. 3.1 Ethanol and bio-ethanol steam reforming. .. al., 2015 Bioenergy Systems for the Future H2 production from bioalcohols and biomethane steam reforming in membrane reactors 3 39 the utilization of renewable alcohols, such as methanol and ethanol,... production from bioalcohols and biomethane steam reforming in membrane reactors 323 hydrogen is industrially produced by steam reforming of natural gas in conventional reactors (CRs) Hence, the reformed