New catalysts for the water gas shift reaction at middle-temperature

H2 demand is continuously increasing since its many relevant applications, for example, in the ammonia production, refinery processes or fuel cells. The Water Gas Shift (WGS) reaction (CO + H2O = CO2 + H2 DeltaH = -41.1 kJ.mol-1) is a step in the H2 production, reducing significantly the CO content and increasing the H2 one in the gas mixtures obtained from steam reforming. Industrially, the reaction is carried out in two stages with different temperature: the first stage operates at high temperature (350-450 °C) using Fe-based catalysts, while the second one is performed at lower temperature (190-250 °C) over Cu-based catalysts. However, recently, an increasing interest emerges to develop new catalytic formulations, operating in a single-stage at middle temperature (MTS), while maintaining optimum characteristics of activity and stability. These formulations may be obtained by improving activity and selectivity of Fe-based catalysts or increasing thermal stability of Cu-based catalysts. In the present work, Cu-based catalysts (Cu/ZnO/Al2O3) prepared starting from hydrotalcite-type precursors show good homogeneity and very interesting physical properties, which worsen by increasing the Cu content. Among the catalysts with different Cu contents, the catalyst with 20 wt.% of Cu represents the best compromise to obtain high catalytic activity and stability. On these bases, the catalytic performances seem to depend on both metallic Cu surface area and synergetic interactions between Cu and ZnO. The increase of the Al content enhances the homogeneity of the precursors, leading to a higher Cu dispersion and consequent better catalytic performances. The catalyst with 20 wt.% of Cu and a molar ratio M(II)/M(III) of 2 shows a high activity also at 250 °C and a good stability at middle temperature. Thus, it may be considered an optimum catalyst for the WGS reaction at middle temperature (about 300 °C). Finally, by replacing 50 % (as at. ratio) of Zn by Mg (which is not active in the WGS reaction), better physical properties were observed, although associate with poor catalytic performances. This result confirms the important role of ZnO on the catalytic performances, favoring synergetic interactions with metallic Cu.

Recycling of end of life concrete fines (0 - 4 mm) into silica and cement

The purpose of this work is to find a methodology in order to make possible the recycling of fines (0 - 4 mm) in the Construction and Demolition Waste (CDW) process. At the moment this fraction is a not desired by-product: it has high contaminant content, it has to be separated from the coarse fraction, because of its high water absorption which can affect the properties of the concrete. In fact, in some countries the use of fines recycled aggregates is highly restricted or even banned. This work is placed inside the European project C2CA (from Concrete to Cement and Clean Aggregates) and it has been held in the Faculty of Civil Engineering and Geosciences of the Technical University of Delft, in particular, in the laboratory of Resources And Recycling. This research proposes some procedures in order to close the loop of the entire recycling process. After the classification done by ADR (Advanced Dry Recovery) the two fractions "airknife" and "rotor" (that together constitute the fraction 0 - 4 mm) are inserted in a new machine that works at high temperatures. The temperatures analysed in this research are 600 °C and 750 °C, cause at that temperature it is supposed that the cement bounds become very weak. The final goal is "to clean" the coarse fraction (0,250 - 4 mm) from the cement still attached to the sand and try to concentrate the cement paste in the fraction 0 - 0,250 mm. This new set-up is able to dry the material in very few seconds, divide it into two fractions (the coarse one and the fine one) thanks to the air and increase the amount of fines (0 - 0,250 mm) promoting the attrition between the particles through a vibration device. The coarse fraction is then processed in a ball mill in order to improve the result and reach the final goal. Thanks to the high temperature it is possible to markedly reduce the milling time. The sand 0 - 2 mm, after being heated and milled is used to replace 100% of norm sand in mortar production. The results are very promising: the mortar made with recycled sand reaches an early strength, in fact the increment with respect to the mortar made with norm sand is 20% after three days and 7% after seven days. With this research it has been demonstrated that once the temperature is increased it is possible to obtain a clean coarse fraction (0,250 - 4 mm), free from cement paste that is concentrated in the fine fraction 0 - 0,250 mm. The milling time and the drying time can be largely reduced. The recycled sand shows better performance in terms of mechanical properties with respect to the natural one.