Chemical Loop Reforming dell'etanolo: studio della reattività di ferriti modificate

Modified ferrites with a generic formula of MFe2O4 (where M=Co, Cu, Mn and their combination: Cu/Co, Cu/Mn and Co/Mn) were studied as potentially attractive ionic oxygen and electron carrier materials for the production of “clean H2” via the Chemical Loop Reforming (CLR) of bio-ethanol. The conventional CLR process consists of 2 steps: 1st - the reduction step with ethanol; 2nd - the re-oxidation step with water. The synthesized materials were tested in a laboratory plant in terms of both redox properties and catalytic activity to generate hydrogen during the re-oxidation step with water steam over previously pre-reduced samples. The obtained results showed that CuFe2O4, Cu0.5Co0.5Fe2O4, Cu0.5Mn0.5Fe2O4 and CoFe2O4 within 20 min of ethanol reduction reached almost a complete reduction, and, as a consequence, the higher yields to H2 produced during the re-oxidation step with steam. On the other hand, incorporation of Mn-cations greatly affects the redox properties of a resulted spinel (MnFe2O4 and Co0.5Mn0.5Fe2O4) leading to its lower reducibility, caused by the formation of a hardly reducible layer of MnxFeyO oxide. Moreover, the presence of Mn-cations effectively reduces the amount of coke formed during the anaerobic reduction step with ethanol and hence avoids a fast deactivation of the material. Modification of the conventional CLR process with an addition of the 3rd regeneration step (carried out with air) was done in order to increase the stability of the looping material and to overcome the deactivation problems, such as: a coke deposition/accumulation and an incomplete re-oxidation of M0 during the 2nd step.

PM and material decay: analysis of dry depositions on horizontal and vertical surrogate surfaces through a Deposition Box system

Airborne Particulate Matter (PM), can get removed from the atmosphere through wet and dry mechanisms, and physically/chemically interact with materials and induce premature decay. The effect of dry depositions is a complex issue, especially for outdoor materials, because of the difficulties to collect atmospheric deposits repeatable in terms of mass and homogeneously distributed on the entire investigated substrate. In this work, to overcome these problems by eliminating the variability induced by outdoor removal mechanisms (e.g. winds and rainfalls), a new sampling system called ‘Deposition Box’, was used for PM sampling. Four surrogate materials (Cellulose Acetate, Regenerated Cellulose, Cellulose Nitrate and Aluminum) with different surfaces features were exposed in the urban-marine site of Rimini (Italy), in vertical and horizontal orientations. Homogeneous and reproducible PM deposits were obtained and different analytical techniques (IC, AAS, TOC, VP-SEM-EDX, Vis-Spectrophotometry) were employed to characterize their mass, dimension and composition. Results allowed to discriminate the mechanisms responsible of the dry deposition of atmospheric particles on surfaces with different nature and orientation and to determine which chemical species, and in which amount, tend to preferentially deposit on them. This work demonstrated that “Deposition Box” can represent an affordable tool to study dry deposition fluxes on materials and results obtained will be fundamental in order to extend this kind of exposure to actual building and heritage materials, to investigate the PM contribution in their decay.