Deamination of Polyols from the Glycolysis of Polyurethane.

Methylenedianiline (MDA) is a secondary, undesired, product of the glycolysis process of polyurethane (PU) scraps due to hydrolysis and pyrolysis side reactions. As an aromatic and carcinogen amine, MDA poses different problems in handling, transporting, and labelling recycled polyols derived from glycolysis, hindering the closure of PU recycling loop. Aiming to provide a solution to this issue, in this work different deaminating agents (DAs) were investigated with the purpose of analyzing their reactivity with MDA. A first part of the study was devoted to the analysis of MDA formation as a function of reaction time and catalyst concentration (potassium acetate) during glycolysis. It was observed that the amount of MDA increases almost linearly with the extent of PU depolymerization and catalyst content. Among the DAs analyzed 2-ethylhexyl glycidyl ether (2-EHGE), and acetic anhydride (Ac2 O) showed interesting performance, which allowed MDA content to be diminished below the limit for labelling prescription in 30 minutes. PU rigid foams were, therefore, synthesized from the corresponding recycled products and characterized in terms of thermal and mechanical performance. Ac2 O-deaminated polyols led to structurally unstable foams with poor compressive strength, while 2-EHGE-deaminated products allowed the production of foams with improved mechanical performance and unaltered thermal conductivity.

Ultrasound-Promoted Abatement of Formaldehyde in Liquid Phase with Electrospun Nanostructured Membranes: The Synergy of Combined AOPs.

The present work investigates the effect of ultrasounds in the performance of combined advanced oxidation processes (AOPs) on the degradation of formaldehyde (HCHO)-polluted aqueous solutions for potential application in wastewater treatment. Different heterogeneous nanostructured catalysts based on TiO2 and FeSO4 for photocatalysis and the Fenton process were employed after electrospray deposition on electrospun nanofibrous membranes. Such systems were tested, without the use of any added hydrogen peroxide, by varying the combinations among the selected AOPs in a batch reactor configuration. The results show that, in the absence of a Fenton reaction, ultrasounds provided a significantly increased formaldehyde photocatalytic abatement, probably by increasing the concentration of active species through a different set of reactions while providing a favorable mass transfer regime by the cavitational effect. Due to the faster kinetics of the photo-Fenton process, thanks to its partial homogeneous nature, such a beneficial effect is more limited for the sono-photo-Fenton configuration. On the other hand, the employment of a sono-photocatalytic-Fenton process revealed a synergic effect that provided the best results, reducing the formaldehyde concentration to less than 99% after 240 min. Further analysis showed that, due to a mutual influence, only a tailored TiO2/FeSO4 ratio on the membranes was able to display the best performance.

Combined AOPs for Formaldehyde Degradation Using Heterogeneous Nanostructured Catalysts.

In this paper we studied the combination of advanced oxidation processes (AOPs), i.e., TiO2-based photocatalysis and photo-Fenton process, on the degradation of aqueous solutions containing a low (90 ppm) concentration of formaldehyde. Heterogeneous nanostructured catalysts, supported on polymeric nanofibers, were used; for comparison, some homogeneous or partly heterogeneous systems were also analyzed. Furthermore, to make the process more sustainable (in terms of costs and safety) no hydrogen peroxide was added to the system. The results showed that the combination of AOPs gave a synergy since the presence of iron was beneficial in promoting the photocatalytic activity of TiO2 while TiO2 was beneficial in promoting the photo-Fenton reaction. Moreover, very good results were obtained using fully heterogeneous nanostructured catalysts (based on TiO2 and FeSO4), without the need to add H2O2.

Structural and Mechanical Characterization of Sustainable Composites Based on Recycled and Stabilized Fly Ash.

This paper reports the results on the use of an innovative inert, based on stabilized fly ash from municipal solid waste incineration as a filler for polypropylene. The starting material, which contains large quantities of leachable Pb and Zn, was stabilized by means of an innovative process using rice husk ash as a waste silica source, together with other fly ashes, such as coal fly ash and flue gas desulfurization residues. The use of all waste materials to obtain a new filler makes the proposed technology extremely sustainable and competitive. The new composites, obtained by using the stabilized material as a filler for polypropylene, were characterized and their mechanical properties were also investigated. A comparison with a traditional polypropylene and calcium carbonate based compound was also done. This research activity was realized in the frame of the COSMOS-RICE project, financed by the EU Commission.