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RESEARCH PROGRAM
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Research Units
Similar research programs:
- 1 - Nanostructured materials based on synthetic hydrotalcites, phosphates and porous oxides and their use in the catalytical reforming of methanol to gaseous mixtures with high hydrogen and low carbon monoxide content.
- 2 - Catalytic/photocatalytic oxidative activation in organic synthesis
- 3 - Sustainable processes of 2nd generation for the production of H2 from renewable resources
- 4 - Nanostructured catalysts for the development of an environmentally friendly process of produce hydrogen on small-medium scale
- 5 - ULTRA-COMPACT STRUCTURED CATALYSTS WITH ITEGRATED HEAT-EXCHANGE SYSTEMS FOR HYDROGEN PRDUCTION
- 6 - Ecofriendly organic syntheses mediated by new catalytic systems
- 7 - INNOVATIVE CATALYTIC PROCESSES FOR THE SELECTIVE OXIDATION AND REDUCTION OF GLYCEROL IN WATER: STUDIES OF REACTION MECHANISMS AND KINETICS FOR THE PROCESS OPTIMISATION
- 8 - Design and development of molecular or nano-structured catalysts and sustainable (high yield and selectivity) synthetic strategies for the synthesis of complex molecular compounds from eco-friendly building blocks.
- 9 - Micro-space confined catalytic combustion
- 10 - Regio- and enantioselective reactions mediated by transition metal catalysts for innovative processes in fine chemicals synthesis
Scientific and education field classification
- Field: Scienze chimiche
- Field: Ingegneria industriale e dell'informazione
International Patent Classification
- CHEMISTRY; METALLURGY
- INORGANIC CHEMISTRY (processing powders of inorganic compounds preparatory to the manufacturing of ceramic products C04B35/00; fermentation or enzyme-using processes for the preparation of elements or inorganic compounds except carbon dioxide C12P3/00; obtaining metal compounds from mixtures, e.g. ores, which are intermediate compounds in a metallurgical process for obtaining a free metal C21B, C22B; production of non-metallic elements or inorganic compounds by electrolysis or electrophoresis C25B)
- COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F (metal hydrides [N: monoborane, diborane or addition complexes thereof] C01B6/00; salts of oxyacids of halogens C01B11/00; peroxides, salts or peroxyacids C01B15/00; thiosulfates, dithionites, polythionates C01B17/64; compounds containing selenium, or tellurium C01B19/00; binary compounds of nitrogen with metals C01B21/06; azides C01B21/08; [N: compounds containing nitrogen, other non-metals and metal C01B21/082]; metal amides C01B21/092; nitrites C01B21/50; [N: compounds of noble gases C01B23/00B]; phosphides C01B25/08; salts of oxyacids of phosphoru C01B25/16; carbides C01B31/30; compounds containing silicon C01B33/00; compounds containing boron C01B35/00; compounds having molecular sieve properties but not having base-exchange properties C01B37/00; compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites, C01B39/00; cyanides C01C3/08; salts of cyanamide C01C3/16; thiocyanates C01C3/20) [C9602]
- NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; [N: METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C] [C9510]
- INORGANIC CHEMISTRY (processing powders of inorganic compounds preparatory to the manufacturing of ceramic products C04B35/00; fermentation or enzyme-using processes for the preparation of elements or inorganic compounds except carbon dioxide C12P3/00; obtaining metal compounds from mixtures, e.g. ores, which are intermediate compounds in a metallurgical process for obtaining a free metal C21B, C22B; production of non-metallic elements or inorganic compounds by electrolysis or electrophoresis C25B)
Geographical classification
- Region: Umbria
Bibliografia
1. (a) A. Turner, “Sustainable Hydrogen Production”, Science, 305 (2006) 972 ; (b) S. S. Penner, Steps towards the energy economy” Energy, 31 (2006) 33.2 J.Agrell, H Birgersson, M. Boutonnet, I. Melián-Cabrera, R.M., Navarro, J.L.G. Fierro, " Production of hydrogen from methanol over Cu/ZnO catalysts promoted by ZrO2 and Al2O3", J. Catal. 219 (2003) 389.
3. R. J. Farrauto, “Introduction to solid polymer membrane fuel cells and reforming natural gas for production of hydrogen”, Appl. Catal. B:Environmental, 56 (2005) 3
4. E.Y. Garcia, M.A. Laborde, “Hydrogen production by the steam reforming of methanol: thermodynamic analysis”, Int. J. Hydrogen Energy 16 (1991) 307.
5 Caixia Qi, J.C. Amphlett, B.A. Peppley, “Product composition as a function of temperature over NiAl-layered double hydroxide derived catalysts in steam reforming of methanol”, Appl. Catal. A: General 302 (2006) 237.
6 S. Liu, K. Takahashi, K. Fuchigami, K. Uematsu, “Hydrogen production by oxidative methanol reforming on Pd/ZnO: Catalyst deactivation”, Appl. Catal. A: General 299 (2006) 58.
7 N. Iwasa, W. Nomura, T. Mayanagi, S. Fujita, M. Arai, N. Takezawa, “Hydrogen production by steam reforming of methanol”, J. Chem. Eng. Japan 37 (2004) 286.
8. G. Jacobs, B.H. Davis, “In situ DRIFTS investigation of the steam reforming of methanol over Pt/ceria”, Appl. Catal. A:General 285 (2005) 43.
9 I. Ritzkopf, S. Vukojevic, C. Weidenthaler, J.-D. Grunwaldt, F. Schüth, “Decreased CO production in methanol steam reforming over Cu/ZrO2 catalysts prepared by the microemulsion technique”, Appl. Catal. A: General 302 (2006) 215.
10 A. Mastalir, B. Frank, A. Szizybalski, H. Soerijanto, A. Deshpande, M. Niederberger, R. Schomäcker, R. Schlögl, T. Ressler, “Steam reforming of methanol over Cu/ZrO2/CeO2 catalysts: a kinetic study“, J. Catal. 230 (2005) 464.
11 Y. Liu, T. Hayakawa, K. Suzuki, S. Hamakawa, T. Tsunoda, T. Ishii, M. Kumagai,"Highly active copper/ceria catalysts for steam reforming of methanol", Appl. Catal. A: General 223 (2002) 137.
12 Shishido, Tetsuya; Yamamoto, Yoshihiro; Morioka, Hiroyuki; Takaki, Ken; Takehira, Katsuomi, „Active Cu/ZnO and Cu/ZnO/Al2O3 catalysts prepared by homogeneous precipitation method in steam reforming of methanol“, Appl. Catal. A: General 263 (2004) 249.
13 Shan, Wenjuan; Feng, Zhaochi; Li, Zhonglai; Zhang, Jing; Shen, Wenjie; Li, Can, “Oxidative steam reforming of methanol on Ce0.9Cu0.1OY catalysts prepared by deposition–precipitation, coprecipitation, and complexation–combustion methods”, J. Catal. 228 (2004) 206.
14 Papavasiliou, Joan; Avgouropoulos, George; Ioannides, Theophilos, “Production of hydrogen via combined steam reforming of methanol over CuO–CeO2 catalysts”, Catal. Commun. 5 (2004) 231.
15 C.-Z. Yao, L.-C. Wang, Y.-M. Liu, G.-S. Wu, Y. Cao, W.-L- Dai, H.-Y. He, K.-N. Fan, “Effect of preparation method on the hydrogen production from methanol steam reforming over binary Cu/ZrO2 catalysts” Appl. Catal. A: General 297 (2006) 151
16 T. Tanabe, S. Kameoka, A. P. Tsai, “A novel catalyst fabricated from Al–Cu–Fe quasicrystal for steam reforming of methanol” Catal. Today 111 (2006) p. 153
17 H. Purnama, F. Girgsdies, T. Ressler, J.H. Schattka, R.A.Caruso, R. Schomäcker, R. Schlögl, “Activity and selectivity of nanostructured CuO/ZrO2 catalyst in the steam reforming of methanol”, Catal. Letters 94 (2004) 61.
18 M.Turco, G.Bagnasco, U.Costantino, F. Marmottini, T. Montanari, G. Ramis, G. Busca, “Production of hydrogen from oxidative steam reforming of methanol: I. Preparation and characterization of Cu/ZnO/Al2O3 catalysts from a hydrotalcite-like LDH precursor” J. Catal 228 (2004) 43
19 M.Turco, G.Bagnasco, U.Costantino, F. Marmottini, T. Montanari, G. Ramis, G. Busca, “Production of hydrogen from oxidative steam reforming of methanol: II. Catalytic activity and reaction mechanism on Cu/ZnO/Al2O3 hydrotalcite-derived catalysts J. Catal 228 (2004) 56
20 U.Costantino, F. Marmottini, M. Sisani, T. Montanari, G. Ramis, G. Busca, M.Turco, G.Bagnasco, “Cu–Zn–Al hydrotalcites as precursors of catalysts for the production of hydrogen from methanol” Solid State Ionics 176, (2005) 2917
21 S. Murcia-Mascarós, R. M. Navarro, L. Gómez-Sainero, U. Costantino, U., M. Nocchetti, J.L.G. Fierro, "Oxidative Methanol Reforming Reactions on CuZnAl Catalysts Derived from Hydrotalcite-like Precursors", J. Catal. 198 (2001) 338
22 S. Velu, K. Suzuki, M.P. Kapoor, F. Ohashi, T. Osaki,"Selective production of hydrogen for fuel cells via oxidative steam reforming of methanol over CuZnAl(Zr)-oxide catalysts", Appl. Catal. A:General, 213 (2001) 47
23. U. Costantino, F. Marmottini, M. Nocchetti, R. Vivani, “New synthetic routes to hydrotalcite-like compounds. Characterization and properties of the obtained materials”, Eur. J. Inorg. Chem., (1998) 1439.
24. M. Turco, G. Bagnasco, U. Costantino, M. Sisani, T. Montanari,G. Ramis, G. Busca, “Cu-ZnO-Al2O3 catalysts for OSRM process: the influence of different synthesis conditions of the LDH precursors”, inviato al First Mediterranean Congress Chemical Engineering for Environment, Venezia 4-6 ottobre 2006.
25. G. M. Lombardo, G. C. Pappalardo, F. Punzo, F. Costantino, U. Costantino, M. Sisani, “A novel Integrated Approach X-Ray Powder Diffraction (XRPD) and Molecular Dynamics (MD) for Modelling Mixed-Metals (Zn, Al) Layered Double Hydroxides (LDH)”, Eur. J. Inorg. Chem. (2005) 5026.
26. F. Frusteri, S. Freni, L. Spadaro, V. Chiodo, G. Bonura, S. Donato, S. Cavallaro, “H2 production for MC fuel cell by steam reforming of ethanol over MgO supported Pd, Rh, Ni and Co catalysts”, Catal. Commun. 5 (2004) 611.
27. V. Fierro, O. Akdim, C. Mirodatos, “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 (2003) 20.
28. J.P. Breen, R. Burch, H.M. Coleman, “Metal-catalysed steam reforming of ethanol in the production of hydrogen for fuel cell applications”, Appl. Catal. B: Environ. 39 (2002) 65.
29. C. Diagne, H. Idriss, A. Kiennemann, “Hydrogen production by ethanol reforming over Rh/CeO2–ZrO2 catalysts”, Catal. Commun. 3 (2002) 565.
30. F. Haga, T. Nakajima, K. Yamashita, S. Mishima, “Effect of crystallite size on the catalysis of alumina-supported cobalt catalyst for steam reforming of ethanol”, React. Kinet. Catal. Lett. 63 (1998) 253.
31. A. Kaddouri, C. Mazzocchia, “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 (2004) 339.
32. J. Llorca, P.R. de la Piscina, J.-A. Dalmon, J. Sales, N. Homs, “CO-free hydrogen from steam-reforming of bioethanol over ZnO-supported cobalt catalysts: Effect of the metallic precursor”, Appl. Catal. B: Environ. 43 (2003) 355.
33. S. Cavallaro, S. Freni, “Ethanol steam reforming in a molten carbonate fuel cell. A preliminary kinetic investigation”, Int. J. Hydrogen Energy 21 (1996) 465.
34. Chen, L., Chang, B.K., Lu, Y., Yang, W., Tatarchuk, B.J., " Selective catalytic oxidation of CO for fuel cell application", Abstracts of Papers, 224th ACS Meeting, Boston, MA, August 18-22, 2002 (2002). CAN: 2002:616820.
35 C.Bracchini, V.Indovina, S. De Rossi, L. Giorgi, "Anodic catalysts for polymer electrolyte fuel cells: the catalytic activity of Pt/C, Ru/C and Pt-Ru/C in oxidation of CO by O2", Catal. Today 55 (2000), 45
36 M. Watanabe, H. Uchida, K. Ohkubo, H. Igarashi, "Hydrogen purification for fuel cells: selective oxidation of carbon monoxide on Pt-Fe/zeolite catalysts", Appl. Catal. B: Environmental 46 (2003), 595.
37. G.Avgouropoulos, T. Ioannides, C. Papadopoulou, J. Batista, S. Hocevar, H. Matralis, "A comparative study of Pt/?-Al2O3, Au/a-Fe2O3 and CuO–CeO2 catalysts for the selective oxidation of carbon monoxide in excess hydrogen", Catal. Today 75 (2002), 157.
Keywords
SYNTHETIC HYDROTALCITES, METALOXIDES FROM HYDROTALCITES, MESOPOROUS OXIDES, NANOSTRUCTURED METAL CATALYSTS, MULTIFUNCTIONAL CATALYSTS, ALCOHOLS REFORMING, HYDROGEN FOR FUEL CELLS, SPECTROSCOPIC CHARACTERIZATION, COMPUTATIONAL CHEMISTRYCatalytic innovative materials and systems for the production of highly pure hydrogen by methanol and ethanol reforming reactions
Università degli Studi di PerugiaAbstract
The project deals with the preparation and study of innovative catalysts for H2 production by reforming reactions of methanol (SRM) and ethanol (SRE). The use of bio-alcohols, such as ethanol and, in some measure, methanol, plays a key role for the possibility to produce hydrogen from renewable sources. The methanol reforming has a central interest for the production of highly pure hydrogen to feed proton exchange membrane fuel cells (PEMFC) for electric cars, while ethanol reforming, that produces hydrogen and an appreciable amount of CO, can be used to feed fuel cells in low and medium power fixed plants.The catalysts should promote the reforming reactions to give high yields of hydrogen, at the lowest possible temperature, with traces of by-products and would be stable for long time with a high specific power.
In order to achieve these ambitious aims, the research program focuses on the preparation, chemical and physical characterization, design and modeling of the catalysts, and on their use in laboratory plants. In particular, the program plans to study the catalysts obtained by precursors based on layered hydrotalcite-like compounds having, in addition to Zn(II), or Mg(II), and Al(III), reducible catalytically active metal ions: Cu, Pt, Pd for methanol and Co, Ni or noble metals for ethanol reforming reactions. The versatility of hydrotalcite-like compounds and the different synthetic procedures will allow to obtain materials having different >>>
Principal Investigator
Umberto Costantino Università degli Studi di PERUGIAResearch Objectives
Fuel cell (FC) technology will become of strategic importance if the processes of hydrogen production have sustainable energetic costs and low environmental impact. The possibility to obtain hydrogen by bio-alcohols, such as ethanol, will allow to use renewable resources. On principle, methanol may be obtained from bio-mass too (it is also a by-product of the fermentation process to obtain ethanol) and may be ascribed to the category of bio-alcohols: reforming of methanol (which today is mostly obtained from synthesis gas, produced from natural gas) has a key role in the application of Proton Exchange Membrane FCs to electric cars and it is considered the most convenient solution to the problem of hydrogen supply. Ethanol reforming, on the other hand, is becoming a process of growing interest to supply fixed plants of FCs, of low and medium power, with hydrogen, instead of the reforming of fossil fuels. Notwithstanding the wide research in this sector, an economical process and a catalyst with optimal performances to produce hydrogen streams suitable to feed the FCs has not yet discovered. The objective of the present research project is the synthesis of new catalysts for the bio-alcohols reforming and for the Preferential Oxidation of CO in order to remove it from the reforming effluents. According to the project, the catalysts will be considered innovative if they possess some key characteristics. In particular the catalysts should:- produce hydrogen with a high >>>
Timescale
24 monthsNational and international background
Energetic problem and fuel cells.At present, the energy demand is satisfied for 80% with non-renewable resources and mostly from fossil fuel. The increasing interest toward alternative energy sources, especially turned to reduce the environmental pollution and greenhouse effect, places hydrogen as one of best promising fuel for the future, for a series of accounts.
It is present in nature with great abundance, it owns the greatest energy density(120700 kJ/kg) and its combustion is really clean, because it produces only water, either when used as fuel in internal combustion apparatus, or employed to feed electrochemical cells.
The use on a large scale of gaseous hydrogen involves big problems to be solved, in order to represent a valid alternative in next future [1].
These problems are connected with its production, storage and distribution. At present, UE Commission in some of its programs, as “Hydrogen platform”, points out that a large scale use of hydrogen must involve a not polluting production and its conversion in electric energy in fuel cells operating either on intermittent charge application, as in electric cars, residential and civil buildings, portable devices, or continuous charge applications, as in stationary systems, or in energy-heat combined cycle systems (CHP).
Among the cells first type we can mention:
Proton Exchange Membrane Fuel Cells (PEMFCs):
the electrolyte is a polymeric membrane which allows the >>>
