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Hydrogen production for fuel cell applications by catalytic partial oxidation of HC- and bio-fuels

Energy scenarios for the next decades predict a growing use of fuel cells for stationary and mobile applications;  this in turn calls for the development of technologies for the delocalized generation of H2-rich streams.  Fossil fuels and biomass derived fuels are both H2-sources of practical interest for stationary and on-board applications, including natural gas, LPG, gasoline and diesel fuels, biogas, oxygenates such as those derived from the valorization of biomass (e.g. alcohols, and organic acids).

Catalysis plays a key role in the development of suitable processes for the small-scale production of H2. Due to economies of scale, the need for compact and fast-response devices make the conventional production routes unsuitable, and innovative solutions are required. In this respect, catalytic processes, such as partial oxidation and autothermal reforming, combine high throughputs and fast dynamics with simple and compact reactors, thereby becoming valid alternatives.
On these topics, the Laboratory of Catalysis and Catalytic Processes has developed several research activities within both industrial and public projects; the focus has been on the short-contact-time Catalytic Partial Oxidation (CPO) of hydrocarbons and oxygenates for the production of H2/CO mixtures, particularly in view of the integration with Solid Oxides Fuel Cells. Several fuels have been studied: methane and light HCs, liquid HCs, olefins, alcohols, ethers and acids. Catalytic systems based on group VIII noble metals, with Rh and Pt being the most promising elements, have been chosen in LCCP labs as reference formulations, since they give optimal performances with good resistance against carbon formation.

The main aims that research has pursued include:
1) the comprehension of the relationships between the surface properties and the activity of the catalytic materials employed;
2) the development of practical and rigorous kinetic schemes to be used for design and analysis purposes;
3) the identification of the key parameters that influence the steady state and transient behaviour of CPO autothermal reformers;
4) the mathematical modelling of the process, with a consistent description of the thermodynamic, kinetic and transport phenomena that occur in the system;
5) the development of a thermoconsistent microkinetic model for CH4 activation on Rh, using a hierarchical multiscale approach, based on fundamental surface chemistry;
6) the detailed analysis of catalytic mechanism of CH4 activation on Rh, elucidating the main reaction pathways occurring under different operating conditions relevant to the process;

In light of these goals, the research activity involves the detailed characterization of the materials, the kinetic study of the CPO reaction in dedicated micro-reactors, as well as the demonstration of the process in an adiabatic pilot scale reformer equipped with structured catalysts and advanced diagnostic techniques. In order to rationalize results obtained under such different scales of study and operation (from the catalytic metal nanoparticle to the fuel processor), a multidisciplinary approach is required, which closely combines experimental and numerical tools.

Faculty members who are involved in the project are: Alessandra Beretta, Alessandro Donazzi, Pio Forzatti, Gianpiero Groppi, Matteo Maestri, Enrico Tronconi.