Nickel-substituted Ba-hexaaluminates as catalysts stem-reforming of tars (2013)

Gasification of woody biomass converts the solid organic material into a gaseous product with a higher energy value and by this mean provide a more carbon neutral gaseous fuel than the common fossil ones. The produced raw gas mainly contains H2, CO, CO2, CH4, H2O and N2 together with organic (tars) and inorganic (alkali) components and fine particulates. The amount of impurities in the raw gas is dependent of the fuel properties and the gasification process technology and the quality of the resulting product gas determines its suitability for more advanced purposes. One of the major general concerns within the gasification processes is the formation of tars. Tars are a vast group of polyaromatic hydrocarbons and there are a number of definitions. On an EU/IEA/US-DOE discussion meeting in Brussels 1998, a number of experts agreed on a simplified classification of tars as “all organic contaminants with a molecular weight larger than benzene” [1]. The aim of this work is to investigate the steam reforming ability of a catalytic material not previously tested in this type of application in order to achieve an energy-efficient and high-quality gasification gas. The physical demands for an optimal tar-cracking and steam reforming catalyst is a high surface area, thermal stability, mechanical strength and a capacity to withstand high gas velocities, poisons such as H2S or NH3 and other impurities. Additionally it has to resist the process steam, as steam is well known to enhance sintering of porous materials. Nickel is a familiar catalyst for steam reforming. Hexaaluminate is a well-known catalyst support with properties that may answer to the requests of a non-abrasive, high-temperaturestable and steam-resistant catalytic material. It is a structural oxide where the general formula for the doped unit cell is MIMII(x)Al12-xO19-d where MI represents the mirror plane cation and MII is the aluminum site in the lattice where substitution may occur. MII is often a transition metal ion of the same size and charge as aluminum. MI is an ion located in the mirror plane of the structure and it is a large metal ion, often from the alkaline, alkaline earth or rare earth metal group. The stability and activity of these materials are often being related to the properties of MI and MII. The activity is highly dependent on the nature of the Al-substituted metal and partially by the nature of MII [2]. In our experiments we have tested the catalytic capacity of Ni-substituted Ba-hexaaluminates synthesised by the sol-gel method [3], both in a model set-up and in a gasification plant. In the lab-scale set-up different catalyst-formulae was tested under various temperatures for reforming of methyl-naphthalene. The results show a good catalytic activity for tar-breakdown. As expected the substitution level of Ni is clearly coupled to the reaction temperature. With the most highly substituted Ni-Bahexaaluminate at 900 °C all of the methyl-naphthalene has been broken downtogether with all of the resulting hydrocarbons. The Ni-Bahexaaluminate catalyst has recently also been tested in real process-gas. These results are still to be evaluated, but indicate a positive result.