Stefano Vecchio Ciprioti

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.

FTIR-evolved gas analysis in recent thermoanalytical investigations

ABSTRACT Several analytical instruments (like pyrolyzers, thermobalances, differential thermal analyzers, or calorimeters, and sometimes simply temperature-controlled reactors) can be on-line coupled to infrared spectrometers to perform evolved gas analysis (EGA). Advances in EGA techniques are currently proposed by the scientific literature because the possibility to on-line detect the nature of the released gases or vapors has become fundamental to proving a supposed reaction, either under isothermal or under heating conditions. In this review, recent analytical applications of evolved gas analysis performed by infrared spectroscopy (EGA-IR), selected among those published in the years 2013 to 2015, are collected.

Characterization of naproxen-polymer conjugates for drug-delivery.

Abstract The synthesis and the characterization of three new naproxen decorated polymers are described. A versatile and general approach is employed to link the drug to polymers, affording the derivatives with a very high degree of purity. The release of the drug from the conjugates proved to be exceptionally slow, even in acidic aqueous media, and the kinetic of the process seems to be triggered by their solubility in water. On the other hand, the interesting outcome of the first ex vivo drug release experiments on human blood samples makes this preliminary study valuable for future investigations on the use of these polymeric prodrugs in in vivo treatment of inflammatory states.

Synthesis, Characterization, and Electrochemical Behavior of LiMnxFe(1−x)PO4 Composites Obtained from Phenylphosphonate-Based Organic-Inorganic Hybrids

The synthesis of organic-inorganic hybrid compounds based on phenylphosphonate and their use as precursors to form LiMnxFe(1−x)PO4 composites containing carbonaceous substances with sub-micrometric morphology are presented. The experimental procedure includes the preliminary synthesis of Fe2+ and/or Mn2+ phenylphosphonates with the general formula Fe(1−x)Mnx[(C6H5PO3)(H2O)] (with 0 < x < 1), which are then mixed at different molar ratios with lithium carbonate. In this way the carbon, obtained from in situ partial oxidation of the precursor organic part, coats the LiMnxFe(1−x)PO4 particles. After a structural and morphological characterization, the electrochemical behavior of lithium iron manganese phosphates has been compared to the one of pristine LiFePO4 and LiMnPO4, in order to evaluate the doping influence on the material.

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.

Sol-Gel Synthesis, Spectroscopic and Thermal Behavior Study of SiO2/PEG Composites Containing Different Amount of Chlorogenic Acid

In this work, new phenol-based materials have been synthesized by the sol-gel method, in which different amounts of the phenolic antioxidant chlorogenic acid (CGA) (from 5 wt % to 20 wt %) were embedded in two different silica matrices: pure silica and silica-based hybrids materials, containing 50 wt % of polyethylene glycol (PEG). The incorporation of CGA in different sol-gel matrices might protect them from degradation, which could cause the loss of their properties. The two series of materials were chemically characterized by Fourier transform infrared (FTIR) spectroscopy. In addition, the thermal behavior of both series of materials containing CGA was studied by thermogravimetry under both air and inert N2 flowing gas atmosphere. The bioactivity was evaluated by soaking the synthesized hybrids in a simulated body fluid, showing that the bioactivity of the silica matrix is not modified by the presence of PEG and CGA.

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.

Sol–gel synthesis and thermal behavior of bioactive ferrous citrate–silica hybrid materials

Imbalance of the iron level in the body causes several diseases. In particular, the low level of iron, during pregnancy, is responsible for the iron deficiency anemia, and even of neurodegenerative diseases. Although the treatment of iron deficiency anemia with oral iron supplements has been known, this problem still afflicts many people. The aim of this work was the development of a system able to release ferrous ions in a controlled manner. Controlled drug release for medical applications, indeed, appears to be a very interesting alternative to a systemic therapy because it is assurance of treatment continuity and drug stability and optimizes drug absorption. For this purpose, ferrous citrate (Fe(II)C) was synthesized by a redox reaction between iron powder and citric acid. Fourier transform infrared spectroscopy (FTIR), 1,10-phenanthroline and sodium thiocyanate colorimetric assays confirmed that only Fe(II)C was obtained by redox reaction. Afterward, obtained Fe(II)C was embedded within a SiO2 matrix in different mass percentage, by means of a sol–gel route. FTIR spectroscopy and simultaneous thermogravimetry/first-order derivative of thermogravimetry were used to confirm the Fe(II)C presence in the silica matrix and to investigate the thermal behavior of the sol–gel materials, respectively. The bioactivity test carried out by soaking the synthesized drug delivery systems in a simulated body fluid showed that the biological properties of the silica matrix are not modified by the presence of Fe(II)C.