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International audience; Several interstellar molecules are highly reactive unsaturated carbon chains, which are unstable under terrestrial conditions. Laboratory studies in support of their detection in space thus face the issue of how to produce these species and how to correctly model their rotational energy levels. In this work, we introduce a general approach for producing and investigating unsaturated carbon chains by means of selected test cases. We report a comprehensive theoretical/experimental spectroscopic characterization of three species, namely, propadienone, cyanovinylacetylene, and allenylacetylene, all of them being produced by means of flash vacuum pyrolysis of a suitable precursor. For each species, quantum-chemical calculations have been carried out with the aim of obtaining accurate predictions of the missing spectroscopic information required to guide spectral analysis and assignment. Rotational spectra of the title molecules have been investigated up to 400 GHz by using a frequency-modulation millimeter-/submillimeter-wave spectrometer, thus significantly extending spectral predictions over a wide range of frequency and quantum numbers. A comparison between our results and those available in the literature points out the clear need of the reported laboratory measurements at higher frequencies for setting up accurate line catalogs for astronomical searches.

espanolThe continuous research of new functional materials combining both advanced properties and increased sustainability has dramatically risen up in the last decades. Instead of searching for new solutions, composites (formed by a combination of already present materials) are subject of different studies due to their capability of merging the advantages of components. Hence, chitosan, a biowaste-derived biopolymer, has been thermally-converted into chars by pyrolysis treatment. Subsequently, both chitosan and its char are introduced into cementitious matrix forming cement-based composites. The analysis of the mechanical properties of these materials evidenced that char-containing composites show an incipient fracture toughness capability, very appealing for possible structural applications. EnglishLa investigacion continua de nuevos materiales funcionales que combinan propiedades avanzadas y una mayor sostenibilidad ha aumentado dramaticamente en las ultimas decadas. En lugar de buscar nuevas soluciones, los compuestos (formados por una combinacion de materiales ya presentes) estan sujetos a diferentes estudios debido a su capacidad de fusionar las ventajas de los dos componentes. El quitosano, un biopolimero derivado de residuos biologicos, se ha convertido termicamente en carbon mediante tratamiento de pirolisis. Posteriormente, tanto el quitosano como su carbon se introducen en una matriz cementosa que forma compuestos a base de cemento. El analisis de las propiedades mecanicas de estos materiales puso de manifiesto que los compuestos que contienen carbon muestran una incipiente capacidad de resistencia a la fractura, muy atractiva para posibles aplicaciones estructurales.

Chemical recycling by thermo-catalytic pyrolysis/degradation offers the possibility of converting waste plastics into their original monomers or other valuable chemicals which can be used as feedstocks in chemical and petrochemical industries. Plastic wastes of polystyrene (PS) based materials can be a good source of styrene as well as mono-aromatic (BTEX: benzene, toluene, ethylbenzene, xylenes) compounds. The selectivity of pyrolysis products can be tuned by choosing the right catalyst as well as appropriate operating conditions/operation modes. In this regard, the focus of the present work was to perform thermo-catalytic pyrolysis of different waste polystyrene (WPS) feedstocks over acid and base catalysts employed in ex-situ and in-situ modes. The main goal was to compare the compositions of pyrolysis products obtained by changing feedstocks, catalysts and operation modes. A further goal was to discuss the suitability of the catalysts employed for the enhanced recovery of desired products from WPS pyrolysis. It was demonstrated that expanded polystyrene gives very similar product distribution as compared to virgin PS, both giving high styrene content. Likewise, hard PS-based random packing materials produce similar results as compared to high impact polystyrene (HIPS). Moreover, it was shown that solid base catalysts influence the composition of the pyrolysis products only slightly as compared to thermolysis. Solid acid catalyst however, showed significant impact on the composition of the pyrolysis products as compared to non-catalytic pyrolysis. These results may provide new insights for the chemical recycling of plastic wastes.

Nowadays, face masks play an essential role in limiting coronavirus diffusion. However, their disposable nature represents a relevant environmental issue. In this work, we propose the utilization of two types of disposed (waste) face masks to prepare hard carbons (biochar) by pyrolytic conversion in mild conditions. Moreover, we evaluated the application of the produced hard carbons as anode materials in Na-ion batteries. Pristine face masks were firstly analyzed through infrared spectroscopy and thermogravimetric analysis. The pyrolysis of both mask types resulted in highly disordered carbons, as revealed by field-emission scanning electron microscopy and Raman spectroscopy, with a very low specific surface area. Anodes prepared with these carbons were tested in laboratory-scale Na-metal cells through electrochemical impedance spectroscopy, cyclic voltammetry and galvanostatic cycling, displaying an acceptable specific capacity along a wide range of current regimes, with a good coulombic efficiency (>98% over at least 750 cycles). As a proof of concept, the anodes were also used to assemble a Na-ion cell in combination with a Na3V2(PO4)2F3 (NVPF) cathode and tested towards galvanostatic cycling, with an initial capacity of almost 120 mAhg−1 (decreasing at about 47 mAhg−1 after 50 cycles). Even though further optimization is required for a real application, the achieved electrochemical performances represent a preliminary confirmation of the possibility of repurposing disposable face masks into higher-value materials for Na-ion batteries.

A synthetic mixture of real waste packaging plastics representative of the residue from a material recovery facility (plasmix) was submitted to thermal and catalytic pyrolysis. Preliminary thermogravimetry experiments coupled with Fourier transform infrared spectroscopy were performed to evaluate the effects of the catalysts on the polymers’ degradation temperatures and to determine the main compounds produced during pyrolysis. The thermal and catalytic experiments were conducted at 370°C, 450°C and 650°C using a bench scale reactor. The oil, gas, and char yields were analyzed and the compositions of the reaction products were compared. The primary aim of this study was to understand the effects of zeolitic hydrogen ultra stable zeolite Y (HUSY) and hydrogen zeolite socony mobil-5 (HZSM5) catalysts with high silica content on the pyrolysis process and the products’ quality. Thermogravimetry showed that HUSY significantly reduces the degradation temperature of all the polymers—particularly the polyolefines. HZSM5 had a significant effect on the degradation of polyethylene due to its smaller pore size. Mass balance showed that oil is always the main product of pyrolysis, regardless of the process conditions. However, all pyrolysis runs performed at 370°C were incomplete. The use of either zeolites resulted in a decrease in the heavy oil fraction and the prevention of wax formation. HUSY has the best performance in terms of the total monoaromatic yield (29 wt-% at 450°C), while HZSM5 promoted the production of gases (41 wt-% at 650°C). Plasmix is a potential input material for pyrolysis that is positively affected by the presence of the two tested zeolites. A more effective separation of polyethylene terephthalate during the selection process could lead to higher quality pyrolysis products. [Figure not available: see fulltext.].

The post-treatment of biomass from phytoremediation is not yet a well-established practice due to the risk induced by the presence of Potentially Toxic Elements (PTEs). Pyrolysis is a thermochemical treatment that reduces the volume and weight of contaminated matter producing a combustible vapor phase and a solid residue (char). A key factor enhancing the economic and the environmental sustainability of biomass valorization through pyrolysis is the production of a market value char. A proper choice of the pyrolysis operating conditions should take into account the effect of final temperature on PTEs release, on the char physicochemical properties as well as on the mobility of retained PTEs. In particular, in this work the influence of both the temperature and the plant parts is discussed (branches and leaves of Populus Nigra L. and rhizomes and culms of Arundo donax L.) on the release of Cd, Pb, Cu, and Zn in the temperature range 653–873 K under steam assisted slow pyrolysis conditions. The mobility of the heavy metals retained in the chars was also studied as well as the product yields, the gas composition and char porosity. The results suggested that in presence of Cd it is necessary to operate at low-temperature (lower than 703 K) to obtain a heavy metals free vapor phase fuel, whereas in presence of one or more metals among Pb, Cu, and Zn, it is possible to conduct a pyrolytic treatment at higher temperatures, thus obtaining a char with high BET surface area and lower metals mobility.

This work focuses on the optimization of pyro-gasification process of carbon fiber reinforced polymers (CFRPs) with the aim of recovering carbon fibers (CFs) with properties suitable for the production of new more sustainable composites with high performances. In particular, the pyro-gasification process is carried out on cured CFRPs panels based on both epoxy (EC) and vinyl ester (VC) matrices, which are the two most used resins for CFRPs. The matrix degradation is evaluated via sample's weight loss measurement and the recovered CFs obtained after different time of treatment are analyzed to identify convenient pyro-gasification conditions to avoid damaging of the recovered CFs. The obtained results highlight the importance of the thickness of the composites to be treated for the identification of the more suitable pyro-gasification conditions.

In view of the potential application of pyrolysis-based biotechnologies, it is crucial to look for novel microorganisms able to convert pyrolysis-derived products, in particular bio-oil water-soluble constituent, into valuable compounds. For the first time, this paper proposed a survey on a collection of bacterial, yeast, and fungal strains with well-known industrial properties as well as new bacterial isolates in order to select microbes able to both tolerate bio-oil inhibitors and convert bio-oil into valuable products. This survey found that bio-oil aqueous phase (BOAP) obtained from intermediate pyrolysis could be metabolized as it is by fungal strains whereas several dilutions are needed to do not hamper cell viability of many tested yeast and bacterial isolates. To process BOAP into valuable products, the yeast Saccharomyces cerevisiae L13, selected as the most industrially relevant tested strain, was adopted to convert bio-oil aqueous fraction hydrolysate into ethanol without any detoxification step. The fermenting performances were much greater than those of the benchmark yeast strain and S. cerevisiae L13 proved to be a strong candidate for bioethanol production from BOAP hydrolysates. This study demonstrated that the search for microorganisms is a promising approach to the future development of pyrolysis oil-based biorefinery platforms.

Abstract In this work, the production of low cost and environment friendly anodes for sodium ion batteries is investigated. Algae are selected as bio-source of non-graphitic Hard Carbon (HC) with open structure acting as intercalation active material for Na ions storage. Chlorella vulgaris algae were pyrolyzed at temperatures comprised between 800 and 1100 °C. The decomposition products have been characterized with Scanning Electrode Microscope (SEM) and X-Ray Diffraction (XRD) analyses and their structure compared to one of the synthetic commercial HC. Thermogravimetric analysis (TGA) allowed to assess the decomposition process throughout the selected temperature scan. The obtained algae-derived HC is tested as anodic material for Na-ion battery, investigating the effect of pyrolysis temperature on the electrochemical behaviour. Their performances are compared with respect to a commercial synthetic HC active material. The results allow to consider algae as an environmentally benign and sustainable high added-value material for the production of HC anodes for Na-ion batteries. Graphic abstract

About 80% of the total pollution from ships is caused by operational oil discharges into the sea, often made deliberately and in violation of international rules; the main reasons can be due to cost savings or lack of adequate facilities in ports to receive waste oils. Therefore, reducing waste oil discharges is crucial for a proper protection of the marine environment. In this regard, the paper presents the preliminary feasibility of a particular waste recycling technology, aimed at obtaining marine fuel oil from sludge, through a pyrolysis process to be carried out in a small reactor onboard. The originality of the research consists in the adaptation of pyrolysis to oily waste produced by ships, since this technology is traditionally applied to solid waste and biomass. Furthermore, the plant has to be designed for operation on board the ship, therefore under very different constraints compared to traditional land plants. Although the preliminary lab tests and simulation results in the chemical process are promising enough, there are still some technical criticalities due to the energy optimization of the reactor for an efficient use onboard of the whole system. In addition, the possibility of recycling waste, directly onboard ships, is not yet covered by mandatory regulations, which is why shipowners generally still feel unmotivated to invest in such technologies.

Carbon-fiber-reinforced polymers (CFRPs) are increasingly used in a variety of applications demanding a unique combination of mechanical properties and lightweight characteristics such as automotive and aerospace, wind turbines, and sport and leisure equipment. This growing use, however, has not yet been accompanied by the setting of an adequate recycling industry, with landfilling still being the main management route for related waste and end-of-life products. Considering the fossil-based nature of carbon fibers, the development of recovery and recycling technologies is hence prioritized to address the environmental sustainability challenges in a bid to approach mitigating the climate emergency and achieving circularity in materials’ life cycles. To this aim, we scaled up and tested a novel semi-industrial pilot plant to pyrolysis and subsequent oxidation of uncured prepreg offcuts and cured waste of CFRPs manufacturing. The environmental performance of the process proposed has been evaluated by means of a life cycle assessment to estimate the associated carbon footprint and cumulative energy demand according to three scenarios. The scale-up of the process has been performed by investigating the influence of the main parameters to improve the quality of the recovered fibers and the setting of preferable operating conditions. The pyro-gasification process attested to a reduction of 40 kgCO2eq per kg of recycled CFs, compared to virgin CFs. If the pyro-gasification process was implemented in the current manufacturing of CFRPs, the estimated reduction of the carbon footprint, depending on the composite breakdown, would result in 12% and 15%. This reduction may theoretically increase up to 59–73% when cutting and trimming waste-optimized remanufacturing is combined with circular economy strategies based on the ideal recycling of CFRPs at end-of-life.

Bio-based substances (BBS) obtained from composted urban biowaste and nanosponges obtained from β-cyclodextrins (βCD) were used as green source to produce biochar via pyrolysis performed under mild conditions. Pyrolysis conditions were optimized by means of TGA analysis, and different temperatures of pyrolysis were investigated. The resulting carbonaceous materials were characterized with several physicochemical techniques (elemental analysis, FTIR spectroscopy, XRD, SEM, surface area analysis, and zeta potential measurements). Additionally, the adsorption capacity of such materials was tested toward the removal of charged dyes from aqueous environment. Isothermal experiments carried out at circumneutral pH indicated an important charge-selectivity, which encourages their use as sustainable alternative materials in wastewater purification treatments. Moreover, the analysis of the adsorption capacity as a function of specific surface area of materials suggests the strategy to obtain carbonaceous solids with enhanced capacity in capture of polar molecules.

Obtaining high quality syngas from sewage sludge (SS) means transferring a low-grade SS into a highgrade fuel or raw materials for chemical products. In this study, Fe is added to SS in form of Fe2(SO4)3 to produce an effective and self-sufficient catalyst in order to obtain more syngas and minimize liquid products from SS pyrolysis. The Fe-embedded sewage sludge chars (SSCs) were used as catalysts for volatile reforming at 600 °C. It has been found that the gas yield increases from 15.9 to 35.8 wt% of the SS and that of liquids decreases from 31.9 to 10.2 wt% after volatile reforming with Fe-embedded SSC when Fe was added equal to 7 % in the dried SS. In addition, the content of nitrogen-containing compounds in the oily products decreased. After reforming with Fe-embedded SSC, the molar fractions of syngas combustible components, including H2, CH4 and CO, increase, and the higher heating value of the syngas increased to 17.0 MJ/Nm3 from the original 12.5 MJ/Nm3 obtained from SS pyrolysis at 550 °C. Moreover, the volatile reforming seems to reduce the level of some important syngas pollutants, like H2S, HCl and HCN, even though it was also observed an increase of the contents of SO2, NH3, NO2, HCNO and N2O. Obtaining high quality syngas from sewage sludge (SS) means transferring a low-grade SS into a high-grade fuel or raw materials for chemical products. In this study, Fe is added to SS in form of Fe2(SO4)3 to produce an effective and self-sufficient catalyst in order to obtain more syngas and minimize liquid products from SS pyrolysis. The Fe-embedded sewage sludge chars (SSCs) were used as catalysts for volatile reforming at 600 °C. It has been found that the gas yield increases from 15.9 to 35.8 wt% of the SS and that of liquids decreases from 31.9 to 10.2 wt% after volatile reforming with Fe-embedded SSC when Fe was added equal to 7 % in the dried SS. In addition, the content of nitrogen-containing compounds in the oily products decreased. After reforming with Fe-embedded SSC, the molar fractions of syngas combustible components, including H2, CH4 and CO, increase, and the higher heating value of the syngas increased to 17.0 MJ/Nm3 from the original 12.5 MJ/Nm3 obtained from SS pyrolysis at 550 °C. Moreover, the volatile reforming seems to reduce the level of some important syngas pollutants, like H2S, HCl and HCN, even though it was also observed an increase of the contents of SO2, NH3, NO2, HCNO and N2O.

Chitin (a biopolymer obtained from shellfish industry) was used as precursor for the production of biochars obtained via pyrolysis treatments performed at mild conditions (in the 290–540 °C range). Biochars were physicochemical characterized in order to evaluate the pyrolysis-induced effects in terms of both functional groups and material structure. Moreover, such carbonaceous materials were tested as adsorbent substrates for the removal of target molecules from aqueous environment as well as in solid-gas experiments, to measure the adsorption capacities and selectivity toward CO2. Lastly, biochars were also investigated as possible cathode materials in sustainable and low-cost electrochemical energy storage devices, such as lithium-sulphur (Li-S) batteries. Interestingly, experimental results evidenced that such chitin-derived biochars obtained via pyrolysis at mild conditions are sustainable, low-cost and easy scalable alternative materials suitable for both environmental and energetic applications.

Trideuterated 1-phosphapropyne (CD3CP) has been produced by co-pyrolysis of phosphorus trichloride and esadeuterated ethane. The rotational spectra of CD3CP in the ground and the low-lying vibrational states v8 (CCP bending mode) and 2 v8 have been investigated in the millimeter-wave region. Very accurate values of the quartic centrifugal distortion constants DJ and DJK and of the sextic distortion constants HJK and HKJ have been obtained for the ground state. l-type resonance effects have been taken into account in the analysis of the spectra of the degenerate bending states, so that the energy difference between the v8|l| = 20, and v8|l| = 22 states could be determined, together with a number of spectroscopic constants involved in the l-type resonance. Moreover, for the parent isotopologue CH3CP a new set of excited-state lines (v8 = 1, 2 and v4 = 1) were recorded up to 330 GHz, and a global analysis including all available rotational and rovibrational transitions related to the ground and v8 = 1, 2 states has been performed. A satisfactory fit could only be obtained by making a reassignment of the few transition wavenumbers previously measured for the 2ν80 ← ν8±1 hot band [M.K. Bane et al., J. Mol. Spectrosc. 275 (2012) 9–14]. The experimental work has been combined with quantum-chemical computations. Quadratic and cubic force constants of 1-phosphapropyne have been calculated at MP2 level of theory with a basis set of triple-ζ quality. A semi-experimental equilibrium structure has been derived by correcting experimental ground-state rotational constants by means of theoretical vibration-rotation interaction constants.

This work is focused on the mechanical characterization and fracture surfaces analysis of thermosetting polymers reinforced with short, randomly oriented, recycled carbon fibres (rCFs). This work aims at evaluating fibre/matrix adhesion between recycled CFs-reclaimed via pyrolysis followed by controlled oxidation of the pyrolytic char-and different polymer matrices, namely epoxy and vinyl ester resins. The latter is the main focus in this work, being amongst the most widely used thermosetting resins in SMC processes, which are the typical target for short rCFs. The evaluation of the properties of this new recycled carbon fibre reinforced polymer (rCFRP) has been via thermogravimetric analysis, dynamic mechanical analysis, stress/strain tests in tensile mode, and a subsequent analysis of the fracture surfaces by means of images analysis obtained by macrophotography, Optical Microscopy and Scanning Electron Microscopy. The comparison amongst the results allowed to evaluate the influence of the polymer nature and of the adhesion quality between fibres and polymeric matrix, mainly on the mechanical properties of the rCFRPs.

L’invenzione riguarda un impianto e un metodo per il recupero di fibre di carbonio o di vetro da materiali compositi nei quali dette fibre sono racchiuse in una matrice polimerica. suddetti materiali compositi possono provenire da scarti prodotti in diversi stadi di lavorazione industriale e/o da manufatti giunti al termine del loro ciclo di vita.

The plastic waste disposal strongly raised in importance in the recent past and it is approaching a critical situation worldwide, so requiring putting in practice the criteria of circular economy by avoiding meaningless policy responses against the plastic materials. The world of plastic materials includes a wide range of goods in all the sectors of our life: packaging, construction, biomedicals, etc. The answer to the plastic waste disposal is build an industrial network characterized by reliability, flexibility, sustainability, utility in the industrial cycle and ability to provide useful products to the market. The traditional processes including recycling and energy recovery fulfil only a part of these conditions and need to be assessed in correlation to their real effect on the circular economy such as the uses of the obtained products in the anthroposphere's life cycle, the burdens generated by the processes itself, etc. Among the possible processes that can be more sustainable if compared with the traditional ones, in a real circular economy perspective, those based on thermochemical exploitation of products obtained by plastics are discussed and assessed. The results show that it is possible to transform an expensive and non-resolving plastic waste management system in an industrial network having an intrinsic economic sustainability and, overall, a well-defined role in the economic chain of plastics. The results show that an integration between the present system with the production of petrochemical products, including oil/gasoline/syngas/…, strongly improve the economic performance of the overall waste system, allowing a larger savings of not-renewable resources, a limited greenhouse burden, a release in the market of valuable products instead of poor quality materials and the minimization of waste destined to be landfilled.

Pyrolysis was explored as a technology for depolymerizing and charring starch-based plastic bags in a novel valorization perspective based on a chemical recycling strategy, alternative to anaerobic digestion or composting. The char obtained from the thermal treatment (420°C for 15 h) was sulfonated to give a highly active and recyclable heterogeneous acid catalyst (10 wt% yield based on starch-based plastic bags subjected to pyrolysis), comparable in terms of catalytic activity and reusability to the analog catalyst prepared from potato starch and tested on a model esterification reaction. From pyrolysis liquid of starch-based plastic bags, highly pure terephthalic acid (4 wt% yield) was isolated through self-precipitation, whereas the remaining pyrolysis liquid produced (21 wt%) was solvent-fractionated to give a polar fraction (7 wt% yield) enriched in levoglucosan, and a less polar fraction (14 wt% yield) enriched in monobutenyl adipate and terephthalate.

Thermo-gravimetric analysis coupled to time/temperature-resolved FTIR spectroscopy of evolved gases was used to measure the vinyl alcohol units content in EVOH copolymer. Pure homopolymers were used as references. The quantitative analysis here proposed is based on the calculation of integral profiles relative to FTIR signals of water molecules evolved during the thermal degradation (pyrolysis) of vinyl alcohol units.

In view of the potential use of pyrolysis-based technologies, it is crucial to understand the environmental hazards of pyrolysis-derived products, in particular bio-oils. Here, three bio-oils were produced from fast pyrolysis of pine wood and intermediate pyrolysis of corn stalk and poultry litter. They were fully characterized by chemical analysis and tested for their biodegradability and their ecotoxicity on the crustacean Daphnia magna and the green alga Raphidocelis subcapitata. These tests were chosen as required by the European REACH regulation. These three bio-oils were biodegradable, with 40-60% of biodegradation after 28 days, and had EC50 values above 100mgL(-1) for the crustacean and above 10mgL(-1) for the alga, showing low toxicity to the aquatic life. The toxic unit approach was applied to verify whether the observed toxicity could be predicted from the data available for the substances detected in the bio-oils. The predicted values largely underestimated the experimental values.

Carbon fiber reinforced polymers (CFRPs), with a demand expected to reach 194 ktons by 2022 and a global market increase to $48.7 billion are increasingly popular materials because of their ability to conjugate superior mechanical resistance and lightness, thus allowing their widespread application ranging from aerospace and wind turbines to automotive and sporting goods. A foreseeable consequence is the growth of production scraps and end-of-life composites. Considering the still high cost of the virgin carbon fiber (CF) and a CF demand expected to reach 117 ktons by 2022 (average of 30 €/kg and energetic cost of 183–286 MJ/kg), this review outlines recent advances of the existing methods to recycle cumulative composite wastes, still with many unresolved problems and issues, with emphasis on CF recovery and understanding their retained properties. Finally, a brief overview on the companies that offer carbon fiber reinforced polymer recovery services with the aim of addressing the issue of end of life is presented.

A “cradle-to-grave” life cycle assessment is performed to identify the environmental issues of polyhydroxyalkanoates (PHAs) produced through a hybrid thermochemical-biological process using anaerobically digested sewage sludge (ADSS) as feedstock. The assessment includes a measure of the energy performance of the process. The system boundary includes: (i) Sludge pyrolysis followed by volatile fatty acids (VFAs) production; (ii) PHAs-enriched biomass production using a mixed microbial culture (MMC); (iii) PHAs extraction with dimethyl carbonate; and iv) PHAs end-of-life. Three scenarios differing in the use of the syngas produced by both pyrolysis and biochar gasification, and two more scenarios differing only in the external energy sources were evaluated. Results show a trade-off between environmental impacts at global scale, such as climate change and resources depletion, and those having an effect at the local/regional scale, such as acidification, eutrophication, and toxicity. Process configurations based only on the sludge-to-PHAs route require an external energy supply, which determines the highest impacts with respect to climate change, resources depletion, and water depletion. On the contrary, process configurations also integrating the sludge-to-energy route for self-sustainment imply more onsite sludge processing and combustion; this results in the highest values of eutrophication, ecotoxicity, and human toxicity. There is not a categorical winner among the investigated configurations; however, the use of a selected mix of external renewable sources while using sludge to produce PHAs only seems the best compromise. The results are comparable to those of both other PHAs production processes found in the literature and various fossil-based and bio-based polymers, in terms of both non-biogenic GHG emissions and energy demand. Further process advancements and technology improvement in high impact stages are required to make this PHAs production process a competitive candidate for the production of biopolymers on a wide scale.

The municipal biowaste anaerobic digestate of a typical waste treatment plant is pyrolyzed under a mild condition (i.e., 540 °C) to directly yield N-doped biochar without performing any subsequent functionalization process. The results confirmed the integration of nitrogen heteroatoms within the carbonaceous framework. The morphological characterization, instead, evidenced the formation of a rather dense biochar with a very low surface area.

Pyrolysis is the simplest method to convert bio-based materials into carbonaceous chars. In this study, Na alginate (an aquatic-derived substance isolated from brown algae) is thermally treated under very mild condition (onset temperature). The effectiveness of the conversion has been determined via physicochemical characterizations, showing the possibility of modifying the (bio)polymeric chemical structure just at the beginning of its thermal degradation, guaranteeing an overall energetic beneficial effect.

We report an extension toward the submillimeter domain of the laboratory spectroscopy of the syn and anti conformers of vinyl alcohol, a species that has been detected once in the interstellar medium, in the massive star-forming region Sagittarius B2(N) (Turner, B. E.; Apponi, A. Microwave detection of interstellar vinyl alcohol, CH2CHOH. Astrophys. J. 2001, 561, L207-L210, 10.1086/324762). Spectra were recorded with high accuracy (15-20 kHz) between 245 and 310 GHz by a frequency-modulation spectrometer equipped with a pyrolysis cell. Using these spectra and the refined molecular constants, we have searched for vinyl alcohol in the publicly available spectral line surveys from the ASAI [Astrochemical Surveys at Institut de Radioastronomie Millimétrique (IRAM)] Large Project, whose source sample spans the evolutionary range of a solar-type protostar and covering 75-350 GHz (4-1 mm) in frequency. We report non-detections in all nine sources, derive upper limits to the abundance of both conformers of vinyl alcohol, and comment on possible chemical and physical explanations for the non-detections.

Nano zero-valent iron (nZVI) has been used as an effective catalyst in different reduction reactions. In this work, a synthesis procedure to obtain a carbon based materials with high nZVI content is reported. This synthesis method consists in a carbothermal reduction at 800 °C of Fe3O4 nanoparticles coated with lignin-derived bio-based substances (BBS) as carbon source, which have been previously prepared from the co-precipitation method. The obtained materials were characterized by powder X-ray diffraction (XRD), Mossbauer spectroscopy, thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and magnetization measurements. The concentration of carbon used in the synthesis process was a critical parameter for obtaining high nZVI yield. Nanomaterials with a 77% of α-Fe over the total iron and saturation magnetization (Ms) of 170 emu g−1 were obtained for the best condition.

At-line sampling by solid phase microextraction (SPME) followed by GC-MS analysis was investigated as a fast analytical method to identify and quantify the compounds evolved during intermediate pyrolysis of biomass. A 75 μm carboxen/polidimethylsiloxane (CAR/PDMS) coated fiber in retracted configuration was inserted at-line during pyrolysis at 500 °C with a bench scale fixed bed pyrolyzer of different biomass substrates, lignocellulosic feedstock, agricultural wastes, animal residues and algal biomass. The molecular composition resulting from SPME sampling was compared to the chemical composition of collected pyrolysis liquid, which included the aqueous and organic phase (bio-oil). The storage capacity of the SPME fiber was tested 48 and 96 h after sampling under air atmosphere and vacuum-packed plastic bags. The SPME-GC-MS profiles could be utilized to gather information on the characteristics of pyrolysis process, such as the efficiency of vapor condensation.

Glass fiber-reinforced polyester composite (GFRPs) scraps from manufacturing of polyester laminates were pyrolyzed at 500, 550 and 600°C in an 70 Kg innovative batch pilot plant that processes whole parts. The presence of a hydraulic guard guarantees the safety of the process. The influence of the maximum process temperature on yields and chemical-physical properties of pyrolysis products was investigated: the oil fraction was analysed by GC-MS, Viscometer and XRF, while the gas fraction was monitored online during the entire pyrolysis process by µ-GC. Substantial fractions of methane (20.7 vol %) and hydrogen (11.5 vol %) were produced. The solid residue (glass fibers covered by a thin carbonaceous layer) underwent an oxidative process at 500 and 600°C at different residence times to provide clean glass fibers free of organic residues. The effects of both pyrolysis and oxidative step on the glass fibers, obtained in different process conditions, were evaluated by SEM and Raman spectroscopy.

The microalgae Botryococcus braunii is widely recognized as a potentially important biofuel-feedstock whose commercial exploitation is limited by difficulties with its cultivation and harvesting. In this study, two B. braunii strains, Kossou-4 and Overjuyo-3 were successfully cultured at a 500 l-scale for 60-days. Harvesting by bio-flocculation with Aspergillus fumigatus at an optimum ratio of 1:40 of fungus to microalgal culture resulted in up to 98% recovery of biomass in the two strains. Ultimate analysis (C, N, H, S, ash, high heating value) and pyrolysis (analytical and preparative pyrolysis and GC–MS assays) showed that co-harvesting with fungi did not cause any impairment of the feedstock value of the microalgal biomass. This work represents the first report on the successful culturing and harvesting of these strains at a 500 l-scale using bio-flocculation. The use of A. fumigatus represents an efficient and economical method for the harvest of B. braunii for biofuel production.

Slow pyrolysis (200–650 °C) experiments on citrus residues (orange peel waste “OP” and lemon peel waste “LP”) were carried out in lab scale fixed bed batch reactor. Bio-oil and bio-char obtained by thermal degradation are more stable, more homogeneous and higher energy content fuels when compared to the parent feedstock. Thermogravimetric analysis (TGA) showed higher stability of LP waste, which appears related to the higher lignin content . Mass and energy yields of solid and liquid products (i.e., char and oil) were measured to determine the effects of peak temperature on feedstock. A linear correlation between Gross Calorific Value (GCV), peak temperatures and mass loss (ML) allows easy analytical calculation of energy properties of residues in the range between 200 °C and 325 °C (peak temperatures). Highest GCV and energy density (ED) of bio-chars are obtained at 500 °C peak temperature for both LP and OP residues: ED LP_CHAR = 1.70, ED OP_CHAR = 1.75. Char reactivities were measured in TGA in a nitrogen atmosphere. High temperature chars (500 and 600 °C) showed a higher reactivity than low temperature ones, between 100 °C and 400 °C. This higher reactivity may be explained by the higher thermal conductivity due to higher ash content and higher surface area of high temperature chars. The tars extracted from pyrolytic bio-oil showed GCVs of approximately 19,700 and 17,000 J/g for LP and OP, respectively, independently of pyrolysis peak temperature. Despite the difference in the GCVs, both LP and OP tars show nearly identical FT-IR spectra denoting the presence of very similar chemical species, mainly phenolic, polyaromatics, ketones, ethers and carboxylic acids.

Three biochars were prepared by intermediate pyrolysis from poultry litter at different temperatures (400, 500, and 600 degrees C with decreasing residence times) and compared with biochars from corn stalk prepared under the same pyrolysis conditions. The phytotoxicity of these biochars was estimated by means of seed germination tests on cress (Lepidium sativum L.) conducted in water suspensions (at 2, 5, and 40 g/L) and on biochars wetted according to their water-holding capacity. Whereas the seeds germinated after 72 h in water suspensions with corn stalk biochar were similar to the control (water only), significant inhibition was observed with poultry litter biochars. In comparison to corn stalk, poultry litter generated biochars with higher contents of ash, ammonium, nitrogen, and volatile fatty acids (VFAs) and a similar concentration of polycyclic aromatic hydrocarbons (PAHs). Results from analytical pyrolysis (Py-GC-MS) indicated that nitrogen-containing organic compounds (NCCs) and aliphatic components were distinctive constituents of the thermally labile fraction of poultry litter biochar. The inhibition of germination due to poultry litter biochar produced at 400 degrees C (PL400) was suppressed after solvent extraction or treatment with active sludge. A novel method based on solid-phase microextraction (SPME) enabled the identification of mobile organic compounds in PL400 capable of being released in air and water, including VFAs and NCCs. The higher phytotoxicity of poultry litter than corn biochars was tentatively attributed to hydrophilic biodegradable substances derived from lipids or proteins removable by water leaching or microbial treatments.

Composted urban biowaste-derived substances (BBS-GC) are used as carbon sources for the preparation of carbon-coated magnet-sensitive nanoparticles obtained via co-precipitation method and the subsequent thermal treatment at 550 °C under nitrogen atmosphere. A multitechnique approach has been applied to investigate the morphology, magnetic properties, phase composition, thermal stability of the obtained magnet-sensitive materials. In particular, pyrolysis-induced modifications affecting the BBS-GC/carbon shell were highlighted. The adsorption capacity of such bio-derivative magnetic materials for the removal of hydrophobic contaminants such as polycyclic aromatic hydrocarbons was evaluated in order to verify their potential application in wastewater remediation process. The promising results suggest their use as a new generation of magnet-responsive easily-recoverable adsorbents for water purification treatments. Fil: Nisticò, Roberto. Università di Torino; Italia. Politecnico di Torino; Italia Fil: Cesano, Federico. Università di Torino; Italia Fil: Franzoso, Flavia. Università di Torino; Italia Fil: Magnacca, Giuliana. Università di Torino; Italia Fil: Scarano, Domenica. Università di Torino; Italia Fil: Funes, Israel German Aristoteles. Universidad Nacional del Comahue; Argentina Fil: Carlos, Luciano. Universidad Nacional del Comahue; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte. Instituto de Investigación y Desarrollo en Ingeniería de Procesos, Biotecnología y Energías Alternativas. Universidad Nacional del Comahue. Instituto de Investigación y Desarrollo en Ingeniería de Procesos, Biotecnología y Energías Alternativas; Argentina Fil: Parolo, Maria Eugenia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte. Instituto de Investigación y Desarrollo en Ingeniería de Procesos, Biotecnología y Energías Alternativas. Universidad Nacional del Comahue. Instituto de Investigación y Desarrollo en Ingeniería de Procesos, Biotecnología y Energías Alternativas; Argentina. Universidad Nacional del Comahue; Argentina

In this research, a particular kind of biochar provided by UK Biochar Centre has been added as nanoparticles into cementitious composites. Its principle characteristic lies in the standardization of its process production, that makes it suitable to been used as filler in cement-matrix composites, ensuring the reproducibility of the cement mix (I. Cosentino “The use of Bio-char for sustainable and durable concrete”, 2017). The pyrolysis parameters and the content of carbon in the standardized biochar influenced its efficiency to enhance the mechanical properties of the cement composites: the results, in terms of flexural strength and fracture energy, have been worse than those obtained in previous studies (L. Restuccia “Re-think, Re-use: agro-food and C&D waste for high-performance sustainable cementitious composites”, 2016), in which particles have been produced with higher temperature. However, also with standardized biochar a general enhancement of mechanical properties has been recorded, a sign that they can be used to create new green building materials.

In this study, chitosan and bio-based substances (BBS) obtained from composted biowaste were used as stabilizers for the synthesis of magnet-sensitive nanoparticles (NPs) via coprecipitation method. A pyrolysis treatment was carried out on both biopolymers at 550 °C, and their consequent conversion into a carbon matrix was followed by means of different physicochemical characterization techniques (mainly FTIR spectroscopy and XRD), whereas magnetic properties were evaluated by magnetization curves. The prepared materials were tested in water remediation processes from arsenic (As) species (both inorganic and organic forms). These tests, explained by means of the most common adsorption models, evidenced that the best performances were reached by both materials obtained after pyrolysis treatments, pointing out the promising application of such magnet-sensitive materials as easy-recoverable tools for water purification treatments. Fil: Nisticò, Roberto. Università di Torino; Italia. Politecnico di Torino; Italia Fil: Celi, Luisella R.. Università di Torino; Italia Fil: Bianco Prevot, Alessandra. Università di Torino; Italia Fil: Carlos, Luciano. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte. Instituto de Investigación y Desarrollo en Ingeniería de Procesos, Biotecnología y Energías Alternativas. Universidad Nacional del Comahue. Instituto de Investigación y Desarrollo en Ingeniería de Procesos, Biotecnología y Energías Alternativas; Argentina Fil: Magnacca, Giuliana. Nanostructured Interfaces And Surfaces; Italia. Università di Torino; Italia Fil: Zanzo, Elena. Università di Torino; Italia Fil: Martin, Maria. Università di Torino; Italia