Riccardo Tuffi

Thermal and catalytic pyrolysis of a mixture of plastics from small waste electrical and electronic equipment (WEEE)

Pyrolysis seems a promising route for recycling of heterogeneous, contaminated and additives containing plastics from waste electrical and electronic equipment (WEEE). This study deals with the thermal and catalytic pyrolysis of a synthetic mixture containing real waste plastics, representative of polymers contained in small WEEE. Two zeolite-based catalysts were used at 400°C: HUSY and HZSM-5 with a high silica content, while three different temperatures were adopted for the thermal cracking: 400, 600 and 800°C. The mass balance showed that the oil produced by pyrolysis is always the main product regardless the process conditions selected, with yields ranging from 83% to 93%. A higher yield was obtained when pyrolysis was carried out with HZSM-5 at 400°C and without catalysts, but at 600 and 800°C. Formation of a significant amount of solid residue (about 13%) is observed using HUSY. The oily liquid product of pyrolysis, analysed by GC-MS and GC-FID, as well as by elemental analysis and for energy content, appeared lighter, less viscous and with a higher concentration of monoaromatics under catalytic condition, if compared to the liquid product derived from thermal degradation at the same temperature. HZSM-5 led to the production of a high yield of styrene (17.5%), while HUSY favoured the formation of ethylbenzene (15%). Energy released by combustion of the oil was around 39MJ/kg, thus suggesting the possibility to exploit it as a fuel, if the recovery of chemical compounds could not be realised. Elemental and proximate analysis of char and GC-TCD analysis of the gas were also performed. Finally, it was estimated to what extent these two products, showing a relevant ability to release energy, could fulfil the energy demand requested in pyrolysis.

Pyrolysis of WEEE plastics using catalysts produced from fly ash of coal gasification

Catalytic pyrolysis of thermoplastics extracted from waste electrical and electronic equipment (WEEE) was investigated using various fly ash-derived catalysts. The catalysts were prepared from fly ash by a simple method that basically includes a mechanical treatment followed by an acid or a basic activation. The synthesized catalysts were characterized using various analytical techniques. The results showed that not treated fly ash (FA) is characterized by good crystallinity, which in turn is lowered by mechanical and chemical treatment (fly ash after mechanical and acid activation, FAMA) and suppressed almost entirely down to let fly ash become completely amorphous (fly ash after mechanical and basic activation FAMB). Simultaneously, the surface area resulted increased. Subsequently, FA, FAMB and FAMA were used in the pyrolysis of a WEEE plastic sample at 400°C and their performance were compared with thermal pyrolysis at the same temperature. The catalysts principally improve the light oil yield: from 59 wt.% with thermal pyrolysis to 83 wt.% using FAMB. The formation of styrene in the oil is also increased: from 243 mg/g with thermal pyrolysis to 453 mg/g using FAMB. As a result, FAMB proved to be the best catalyst, thus producing also the lowest and the highest amount of char and gas, respectively.

Thermal Behavior and Structural Study of SiO2/Poly(ε-caprolactone) Hybrids Synthesized via Sol-Gel Method

SiO2-based organic-inorganic hybrids (OIHs) are versatile materials whose properties may change significantly because of their thermal treatment. In fact, after their preparation at low temperature by the sol-gel method, they still have reactive silanol groups due to incomplete condensation reactions that can be removed by accelerating these processes upon heating them in controlled experimental conditions. In this study, the thermal behavior of pure SiO2 and four SiO2-based OIHs containing increasing amount (6, 12, 24 and 50 wt %) of poly(ε-caprolactone) (PCL) has been studied by simultaneous thermogravimetry (TG) and differential scanning calorimetry (DSC). The FTIR analysis of the gas mixture evolved at defined temperatures from the samples submitted to the TG experiments identified the mechanisms of thermally activated processes occurring upon heating. In particular, all samples already release ethanol at low temperature. Moreover, thermal degradation of PCL takes place in the richest-PCL sample, leading to 5-hexenoic acid, H2O, CO2, CO and ε-caprolactone. After the samples’ treatment at 450, 600 and 1000 °C, the X-ray diffraction (XRD) spectra revealed that they were still amorphous, while the presence of cristobalite is found in the richest-PCL material.