Recovery of Terephthalic Acid from Densified Post-consumer Plastic Mix by HTL Process.

In this study, we investigate the hydrothermal liquefaction (HTL) of PET separated from a densified postconsumer plastic mix, with the aim of recovering its monomer. This second raw material is made up of 90% polyolefin, while the remaining 10% is made up of PET, traces of metals, paper, and glass. After preliminary separation by density in water, two batch experiments were performed on the sunken fraction (composed mainly of PET) in a stainless steel autoclave at 345 °C for 30 and 20 min. Both trials resulted in similar yields of the three phases. In particular, the solid yield is around 76% by weight. After a purification step, this phase was analyzed by UV-Vis, 1H-NMR, and FTIR spectroscopy and resulted to be constituted by terephthalic acid (TPA), a product of considerable industrial interest. The study proved that the hydrothermal liquefaction process coupled with density separation in water is effective for obtaining TPA from a densified postconsumer plastic mix, which can be used for new PET synthesis.

Subcritical Hydrothermal Liquefaction as a Pretreatment for Enzymatic Degradation of Polyurethane.

Enzymatic digestion is a promising alternative in the upconversion of plastic waste compared to traditional chemical recycling methods, because it warrants the use of milder conditions. However, enzymes are hardly able to penetrate the bulk of the plastic material; thus, a pretreatment is necessary to promote the reaction. In this study we investigate hydrothermal liquefaction as a thermal pretreatment of a commercial polyurethane before performing an enzymatic digestion. The feedstock is a rigid polyurethane foam. The structure and chemical composition of the feedstock were analyzed through FTIR analysis and solid-state 13C NMR. The polyurethane was then subjected to hydrothermal liquefaction using either ultrapure water or KOH as a basic catalyst. Enzymatic digestion was then performed on the organic fraction obtained from both experiments using a lipase extracted from Candida rugosa. The LC-MS analysis of the digests shows an increase in some signal intensities due to the degradation of oligomeric fragments. This new way of recycling allows the recovery of important chemicals such as quinolines and 4,4'-methylenedianiline. With this study we demonstrate that hydrothermal liquefaction coupled with enzymatic digestion is a suitable alternative for handling polyurethane waste.

Towards a better understanding of the HTL process of lignin-rich feedstock.

The hydrothermal liquefaction reactions (HTL) in subcritical conditions of a lignin residue has been studied on a lab scale. The starting material was a lignin rich residue co-produced by an industrial plant situated in Northern Italy producing lignocellulosic bioethanol. The reactions were carried out in batch mode using stainless steel autoclaves. The experiments were under the following operating conditions: two different temperatures (300-350 °C), the presence of basis catalysts (NaOH, and NH4OH) in different concentrations and the presence/absence of capping agent 2,6-bis-(1,1-dimethylethyl)-4-methylphenol (BHT). Lignin residue and reaction products were characterized by analytical and spectroscopic techniques such as CHN-S, TGA, GC-MS, EPR, and 1H-NMR with (2,2,6,6-Tetramethylpiperidin-1-yl)oxyl (T.E.M.P.O.). The addition of BHT did not significantly affect the yield of char which is formed by radical way. Spectroscopic analysis indicated that the level of radicals during the reaction was negligible. Therefore, the results obtained experimentally suggest that the reaction takes place via an ionic route while radical species would play a minor role.

Nanodispersions of TiO2 in Water for Removing Acrylic Films Used in Conservation.

The influence of a nanodispersion of TiO2 in water (nanoparticle size: 40 nm, polydispersity index: 0.25), brushed on a Paraloid film and subjected to UV-Vis irradiation was evaluated. The TiO2 nanodispersions showed a tendency to reduce the molecular weight of Paraloid due to its photocatalytic properties. FTIR and GPC analyses and SEM images suggested the degradation of the polymer, while chromatic variations of the films were scarcely detected. This study is very remarkable in the perspective of using this material for the removal of polymeric films used in conservation.