Monica Puccini

Effect of sewage sludge content on gas quality and solid residues produced by cogasification in an updraft gasifier.

In the present work, the gasification with air of dehydrated sewage sludge (SS) with 20 wt.% moisture mixed with conventional woody biomass was investigated using a pilot fixed-bed updraft gasifier. Attention was focused on the effect of the SS content on the gasification performance and on the environmental impact of the process. The results showed that it is possible to co-gasify SS with wood pellets (WPs) in updraft fixed-bed gasification installations. However, at high content of sewage sludge the gasification process can become instable because of the very high ash content and low ash fusion temperatures of SS. At an equivalent ratio of 0.25, compared with wood pellets gasification, the addition of sewage sludge led to a reduction of gas yield in favor of an increase of condensate production with consequent cold gas efficiency decrease. Low concentrations of dioxins/furans and PAHs were measured in the gas produced by SS gasification, well below the limiting values for the exhaust gaseous emissions. NH(3), HCl and HF contents were very low because most of these compounds were retained in the wet scrubber systems. On the other hand, high H(2)S levels were measured due to high sulfur content of SS. Heavy metals supplied with the feedstocks were mostly retained in gasification solid residues. The leachability tests performed according to European regulations showed that metals leachability was within the limits for landfilling inert residues. On the other hand, sulfate and chloride releases were found to comply with the limits for non-hazardous residues.

Bioethanol–gasoline fuel blends: Exhaust emissions and morphological characterization of particulate from a moped engine

This study was aimed at evaluating the effects of gasoline–ethanol blends on the exhaust emissions in a catalyst-equipped four-stroke moped engine. The ethanol was blended with unleaded gasoline in at percentages (10, 15, and 20% v/v). The regulated pollutants and the particulate matter emissions were evaluated over the European ECE R47 driving cycle on the chassis dynamometer bench. Particulate matter was characterized in terms of total mass collected on filters and total number of particles in the range 7 nm–10 μm measured by electrical low-pressure impactor (ELPI). In addition, particle-phase polycyclic aromatic hydrocarbons (PAHs) emissions were evaluated to assess the health impact of the emitted particulate. Finally, an accurate morphological analysis was performed on the particulate by high-resolution transmission electron microscope (TEM) equipped with a digital image-processing/data-acquisition system. In general, CO emission reductions of 60–70% were obtained with 15 and 20% v/v ethanol blends, while the ethanol use did not reduce hydrocarbon (HC) and NOx emissions. No evident effect of ethanol on the particulate mass emissions and associated PAHs emissions was observed. Twenty-one PAHs were quantified in the particulate phase with emissions ranging from 26 to 35 μg/km and benzo[a]pyrene equivalent (BaPeq) emission factors from 2.2 to 4.1 μg/km. Both particulate matter and associated PAHs with higher carcinogenic risk were mainly emitted in the submicrometer size range (<0.1 μm). On the basis of the TEM observations, no relevant effect of the ethanol use on the particulate morphology was evidenced, showing aggregates composed of primary particles with mean diameters in the range 17.5–32.5 nm. Implications: Mopeds may contribute in a large share to air pollution in some major urban areas; therefore, efforts may be taken to reduce their emissions. The addition of ethanol into gasoline (up 20% v/v) leads to a significant reduction of CO emission at the exhaust of a catalyzed 4-S moped, whereas this does not reduce HC and NOx. No clear effects on particulate matter and associated PAHs emissions have been observed with ethanol addition, but particulate-phase PAHs were mainly found on submicrometer-size particles (<0.1 μm), which penetrate deeply into the human respiratory tract.

CO2 Capture at High Temperature and Low Concentration on Li4sio4 Based Sorbents

Solid sorbents based on lithium orthosilicate (Li4SiO4) have shown promise for CO2 capture at high temperature. Improved sorption properties can be obtained by appropriate doping. In this study, different promoted Li4SiO4-based sorbents were prepared by addition of potassium carbonate and binary/ternary alkali (Li, K and Na) carbonate eutectic mixtures. The CO2 sorption properties of the sorbents were investigated by thermal gravimetric analysis (TGA) at different temperatures in the range between 500 and 600 °C and at low CO2 partial pressure (0.04 atm). The results showed that all the promoters used noticeably improved the CO2 sorption capacity in comparison to no-promoted Li4SiO4. At the optimum sorption temperature of 580 °C, Li4SiO4 with addition of 30 wt% of K2CO3 showed the best CO2 adsorption proprieties with sorption capacities of 230 mg CO2/g sorbent corresponding to a conversion of about 80 %. Besides this sample maintained its original capacity during multiple CO2 sorption/desorption cycles.

New Bio-Composites Based on Polyhydroxyalkanoates and Posidonia oceanica Fibres for Applications in a Marine Environment

Bio-composites based on polyhydroxyalkanoates (PHAs) and fibres of Posidonia oceanica (PO) were investigated to assess their processability by extrusion, mechanical properties, and potential biodegradability in a natural marine environment. PHAs were successfully compounded with PO fibres up to 20 wt % while, at 30 wt % of fibres, the addition of 10 wt % of polyethylene glycol (PEG 400) was necessary to improve their processability. Thermal, rheological, mechanical, and morphological characterizations of the developed composites were conducted and the degradation of composite films in a natural marine habitat was evaluated in a mesocosm by weight loss measure during an incubation period of six months. The addition of PO fibres led to an increase in stiffness of the composites with tensile modulus values about 80% higher for composites with 30 wt % fibre (2.3 GPa) compared to unfilled material (1.24 GPa). Furthermore, the impact energy markedly increased with the addition of the PO fibres, from 1.63 (unfilled material) to 3.8 kJ/m2 for the composites with 30 wt % PO. The rate of degradation was markedly influenced by seawater temperature and significantly promoted by the presence of PO fibres leading to the total degradation of the film with 30 wt % PO in less than six months. The obtained results showed that the developed composites can be suitable to manufacture items usable in marine environments, for example, in natural engineering interventions, and represent an interesting valorisation of the PO fibrous wastes accumulated in large amounts on coastal beaches.

Eco-friendly titanium tanning for the manufacture of bovine upper leathers: pilot-scale studies

Conventional chrome-tanning process is constantly under pressure from increasingly stringent environmental regulations on discharges of chromium-containing effluents and wastes. For this reason, in the past years alternative chrome-free tanning processes have been developed. Among these, titanium tanning is one of the most promising substitutes for chromium tanning in today’s leather industry. In this study the use of titanyl sulfate masked with citrate was investigated as tanning agent for the production of high-quality bovine upper leather on pilot scale. Preliminary experimental activities were performed to individuate the minimum citrate/titanium mole ratio to ensure a good titanium sulfate solution stability and minimum quantity of salt (sodium chloride) in pickling solution sufficient to depress acidic swelling of the skins. Ti-tanned leathers produced by the developed Ti-tanning process showed comparable physical–mechanical properties to those of traditionally Cr-tanned leathers, used as control, but a lower hydrothermal stability although acceptable. The Ti-tanned leathers complied with the standards for high-quality upper leather exhibiting better dyeability, due to their higher affinity to anionic dyestuffs, and similar softness, fullness, roundness, and hand compared to the control leathers.

Small-scale wood-fuelled CHP plants: A comparative evaluation of the available technologies

Actually, several applications of small (≤1 MWe) CHP (Combined Heat and Power) plants fuelled with solid wood can be found in Europe. Innovative technologies are facing the market, giving new perspectives for wood utilisation in district heating and/or in industrial-commercial activities. However, while the energy saving and the environmental benefits of CHP plants are undoubted, technological and no technological barriers still obstacle their large diffusion. The present study reports a comparative evaluation of the different available technologies in terms of thermal and electric efficiencies and their possible applications. Taking into consideration the electricthermal performances of each configuration and the actual economic incentives guaranteed by the Italian government, a preliminary estimation of economic convenience of each plant is given.

Lithium Silicate Pellets for CO2 Capture at High Temperature

In this study, lithium orthosilicate-based pellets were developed and characterized as potential regenarable high-temperature CO2 sorbents. A mechanical method was used for pelletization of the powdered materials, namely K2CO3-doped lithium silicate (Li4SiO4) with cellulose fibres. Different amounts of cellulose fibres (20, 30 and 40 wt%) were added to powered doped-sorbent in order to identify the optimal amount to ensure an adequate porosity to the produced pellets. The CO2 sorption properties of the produced pellets were investigated at high temperature (500 600 °C) by using a thermal gravimetric analyzer (TGA) at low CO2 partial pressure with repeated calcination/carbonation cycles. Compared to the pure K2CO3-doped lithium silicate pellets, the sorbents prepared using cellulose fibres showed greater CO2 capture capabilities, which were ascribed to the higher porosity developed as a result of thermal degradation of cellulose. At 580 °C and a CO2 partial pressure of 0.04 atm, the uptake of CO2 in pellets prepared with 20 % of cellulose fibres reached about 20 wt% within 120 min corresponding to a Li4SiO4-conversion of 57 %. During multiple sorption/desorption cycles, a decay of the sorption capacity of the pellets was observed due to a partial sintering of the materials. This suggested that an appropriate binder should be added in order to improve the cyclic stability and the strength of the produced pellets.

Life Cycle Assessment of Remediation Alternatives for Dredged Sediments

In this study, LCA was used to compare, in terms of their associated environmental burdens, two scenarios for managing the contaminated dredged sediments of the seabed of the Livorno Port area. The compared options were: (i) confined longshore disposal, i.e. placement of dredged material in a confined disposal facility; (ii) phytoremediation treatment, by an association of salt-tolerant shrub and grass species, aimed at turning the polluted sediment an agronomic substrate (techno-soil). The results of the life cycle impact assessment underline that the potential impacts of the two compared options involve different environmental problems. Indeed, for phytoremediation the most significant impacts are related to energy and resources consumption, while for the confined disposal is related to loads in the marine ecotoxicity categories. Therefore, phytoremediation can be considered a promising alternative solution for the management and valorization of contaminated dredged sediments.

A general environmentally friendly access to long chain fatty acid ionic liquids (LCFA-ILs)

The development of bio-based ionic liquids (ILs) has attracted a great deal of interest in recent years. The so called long chain fatty acid ionic liquids (LCFA-ILs) represent a bio-based subfamily of hydrophobic ionic liquids. Here, a new preparation of the three major classes of LCFA-ILs (phosphonium, ammonium, imidazolium) is presented with the aim to overcome previous environmental synthetic issues. The undeniable interesting properties and potential applications of the LCFA-ILs often led to the underestimation of the drawbacks related to their synthetic pathways. Pure LCFA-ILs as well as cheaper mixture of LCFA-ILs have been obtained in a single step, in almost quantitative yields, and without production of waste water. The rheological and thermal stability properties of the prepared ILs have been analyzed.

Removal of CO2 from flue gas at high temperature using novel porous solids

Since the CO2 separation is the first and most energy intensive step of carbon capture and storage (CCS) technology, many research have targeted at improving the current technologies or developing new approaches of CO2 separation and capture. In this study, lithium orthosilicate-based pellets were developed and characterized as potential regenarable high-temperature CO2 sorbents. A mechanical method was used for pelletization of the powdered materials, namely K2CO3-doped lithium silicate (Li4SiO4). For increasing the performance of the pellets over multiple cycles an activation strategy was applied: the powdered sorbents were pelletized with a binder for enhancing their porosity by applying a thermal activation before adsorption process. Different amounts of binders (layered graphite and carbon nanotubes) were added to powered doped-sorbent in order to identify the optimal amount to ensure an adequate porosity into the pellets. The CO2 sorption properties of the obtained pellets were investigated by using a thermal gravimetric analyzer (TGA) in a controlled gas flow environment at low CO2 partial pressure (0.04 atm). Compared to the pure K2CO3-doped lithium silicate pellets, the sorbents prepared using layered graphite showed greater CO2 capture capabilities, which were ascribed to the higher porosity developed as a result of the activation. At 580 °C and a CO2 partial pressure of 0.04 atm, the uptake of CO2 in pellets prepared with 20 % of graphite reached about 200 mg CO2/g sorbent within 120 minutes corresponding to a Li4SiO4-conversion of 72.1 %. During multiple sorption/desorption cycles, a decay of the sorption capacity of the pellets was observed due to a partial sintering of the materials.