Thermally Stimulated Currents in Nanocrystalline Titania.

A thorough study on the distribution of defect-related active energy levels has been performed on nanocrystalline TiO2. Films have been deposited on thick-alumina printed circuit boards equipped with electrical contacts, heater and temperature sensors, to carry out a detailed thermally stimulated currents analysis on a wide temperature range (5-630 K), in view to evidence contributions from shallow to deep energy levels within the gap. Data have been processed by numerically modelling electrical transport. The model considers both free and hopping contribution to conduction, a density of states characterized by an exponential tail of localized states below the conduction band and the convolution of standard Thermally Stimulated Currents (TSC) emissions with gaussian distributions to take into account the variability in energy due to local perturbations in the highly disordered network. Results show that in the low temperature range, up to 200 K, hopping within the exponential band tail represents the main contribution to electrical conduction. Above room temperature, electrical conduction is dominated by free carriers contribution and by emissions from deep energy levels, with a defect density ranging within 1014-1018 cm-3, associated with physio- and chemi-sorbed water vapour, OH groups and to oxygen vacancies.

Evaluation of the environmental sustainability of different waste-to-energy plant configurations.

Residual municipal solid waste (MSW) has an average lower heating value higher than 10GJ/Mg in the EU, and can be recovered in modern Waste-to-Energy (WtE) plants, producing combined heat and power (CHP) and reaching high levels of energy recovery. CHP is pinpointed as the best technique for energy recovery from waste. However, in some cases, heat recovery is not technically feasible - due to the absence of a thermal user (industrial plant or district heating) in the vicinity of the WtE plant - and power production remains the sole possibility. In these cases, there are some challenges involved in increasing the energy performance as much as possible. High energy recovery efficiency values are very important for the environmental sustainability of WtE plants. The more electricity and heat is produced, the better the saving of natural resources that can be achieved. Within this frame, the aim of this work is to carry out an environmental assessment, through Life Cycle Assessment, of an MSW WtE plant, considering different sizes and operated in different ways, from power production only to full cogeneration. The main assumption is that the electric conversion efficiency increases as the plant size increases, introducing technical improvements thanks to the economies of scale. Impact assessment results were calculated using ReCiPe 2008 methods. The climate change indicator is positive when the WtE plant is operated in power production only mode, with values decreasing for the increasing size. Values for the climate change are negative when cogeneration is applied, requiring increasing cogeneration ratios for decreasing size. Similarly, the fossil fuel depletion indicator benefits from increase of both the plant size and the cogeneration rate, but it is always negative, meaning that the residual MSW burning with energy recovery always provides a saving of fossil primary energy. Other indicator values are in general negative and are also beneficially affected by increasing the plant size, but they worsen when increasing the cogeneration rate. The remaining indicators - i.e. human toxicity and terrestrial ecotoxicity - always have positive values, which decrease for increasing plant size and increase as the cogeneration rate increases. However, the local context should be evaluated carefully with reference to the type of electricity which is substituted and in view of a future massive production of renewable electricity, because conclusions change accordingly. Finally, it was evaluated that the inclusion of bottom ash recovery - instead of landfilling - can significantly improve the values of several impact assessment indicators.

Comparative life cycle assessment of alternative strategies for energy recovery from used cooking oil.

The separate collection of Used Cooking Oil (UCO) is gaining popularity through several countries in Europe. An appropriate management of UCO waste stream leads to substantial benefits. In this study, we analyse two different possibilities of UCO energy reuse: the direct feed to a reciprocating internal combustion engine (ICE) for cogeneration purpose, and the processing to generate biodiesel. Concerning biodiesel production, we analyse four among conventional and innovative technologies, characterised by different type and amount of used chemicals, heat and electricity consumptions and yields. We perform a systematic evaluation of environmental benefits and drawbacks by applying life cycle assessment (LCA) analysis to compare the alternatives. For the impact assessment, two methods are selected: the Global Warming Potential (GWP) and Cumulative Exergy Consumption (CExC). Results related only to the processing phases (i.e. not including yet the avoided effects) show that the recovery of UCO in cogeneration plant has in general lower values in terms of environmental impacts than its employment in biodiesel production. When products and co-products substitution are included, the savings obtained by the substitution of conventional diesel production, in the biodiesel cases, are significantly higher than the avoided effects for electricity and heat in the cogeneration case. In particular, by using the UCO in the biodiesel production processes, the savings vary from 41.6 to 54.6 GJex per tUCO, and from 2270 to 2860 kg CO2eq per tUCO for CExC and GWP, respectively. A particular focus is put on sensitivity and uncertainty analyses. Overall, high uncertainty of final results for process impacts is observed, especially for the supercritical methanol process. Low uncertainty values are evaluated for the avoided effects. Including the uncertain character of the impacts, cogeneration scenario and NaOH catalysed process of biodiesel production result to be the most suitable solutions from the process impacts and avoided effects perspective.

Environmental comparison of alternative treatments for sewage sludge: An Italian case study.

A Life Cycle Assessment (LCA) was applied to compare different alternatives for sewage sludge treatment: such as land spreading, composting, incineration, landfill and wet oxidation. The LCA system boundaries include mechanical dewatering, the alternative treatment, transport, and final disposal/recovery of residues. Cases of recovered materials produced as outputs from the systems, were resolved by expanding the system boundaries to include avoided primary productions. The impact assessment was calculated using the CML-IA baseline method. Results showed that the incineration of sewage sludge with electricity production and solid residues recovery collects the lowest impact indicator values in the categories human toxicity, fresh water aquatic ecotoxicity, acidification and eutrophication, while it has the highest values for the categories global warming and ozone layer depletion. Land spreading has the lowest values for the categories abiotic depletion, fossil fuel depletion, global warming, ozone layer depletion and photochemical oxidation, while it collects the highest values for terrestrial ecotoxicity and eutrophication. Wet oxidation has just one of the best indicators (terrestrial ecotoxicity) and three of the worst ones (abiotic depletion, human toxicity and fresh water aquatic ecotoxicity). Composting process shows intermediate results. Landfill has the worst performances in global warming, photochemical oxidation and acidification. Results indicate that if the aim is to reduce the effect of the common practice of sludge land spreading on human and ecosystem toxicity, on acidification and on eutrophication, incineration with energy recovery would clearly improve the environmental performance of those indicators, but an increase in resource depletion and global warming is unavoidable. However, these conclusions are strictly linked to the effective recovery of solid residues from incineration, as the results are shown to be very sensitive with respect to this assumption. Similarly, the quality of the wet oxidation process residues plays an important role in defining the impact of this treatment.

Leaching behaviour of hazardous waste under the impact of different ambient conditions.

The overall objective of this study is to provide an improved basis for the assessment of the leaching behaviour of waste marked as hazardous partly stabilised (European waste catalogue code 19 03 04∗). Four samples of hazardous partly stabilised waste were subjected to two leaching tests: up-flow column tests and batch equilibrium tests. The research was carried out in two directions: the first aims at comparing the results of the two experimental setups while the second aims at assessing the impact of different ambient conditions on the leaching behaviour of waste. Concerning this latter objective the effect of mesophilic temperature, mechanical constraints and acid environment were tested through column percolation tests. Results showed no significant differences between batch and column leaching test outcomes when comparing average concentrations calculated at a liquid to solid ratio of 10:1 l kg-1 TS. Among the tested ambient conditions, the presence of an acid environment (pH=4.5) accelerated the leaching process resulting in a higher cumulative released quantity measured on the majority of the investigated polluting substances. On the contrary, the effect of temperature and mechanical constraints seemed to not affect the process showing final contents even lower than values found for the standard test. This result was furthermore confirmed by the application of the principal component analysis.

Biochemical methane potential tests of different autoclaved and microwaved lignocellulosic organic fractions of municipal solid waste.

The aim of this research was to enhance the anaerobic biodegradability and methane production of two synthetic Organic Fractions of Municipal Solid Waste with different lignocellulosic contents by assessing microwave and autoclave pre-treatments. Biochemical Methane Potential assays were performed for 21days. Changes in the soluble fractions of the organic matter (measured by soluble chemical oxygen demand, carbohydrates and proteins), the first order hydrolysis constant kh and the cumulated methane production at 21days were used to evaluate the efficiency of microwaving and autoclaving pretreatments on substrates solubilization and anaerobic digestion. Microwave treatment led to a methane production increase of 8.5% for both the tested organic fractions while autoclave treatment had an increase ranging from 1.0% to 4.4%. Results showed an increase of the soluble fraction after pre-treatments for both the synthetic organic fractions. Soluble chemical oxygen demand observed significant increases for pretreated substrates (up to 219.8%). In this regard, the mediocre results of methane's production led to the conclusion that autoclaving and microwaving resulted in the hydrolysis of a significant fraction of non-biodegradable organic substances recalcitrant to anaerobic digestion.

A review of technologies and performances of thermal treatment systems for energy recovery from waste.

The aim of this work is to identify the current level of energy recovery through waste thermal treatment. The state of the art in energy recovery from waste was investigated, highlighting the differences for different types of thermal treatment, considering combustion/incineration, gasification and pyrolysis. Also different types of wastes - Municipal Solid Waste (MSW), Refuse Derived Fuel (RDF) or Solid Refuse Fuels (SRF) and some typologies of Industrial Waste (IW) (sludge, plastic scraps, etc.) - were included in the analysis. The investigation was carried out mainly reviewing papers, published in scientific journals and conferences, but also considering technical reports, to gather more information. In particular the goal of this review work was to synthesize studies in order to compare the values of energy conversion efficiencies measured or calculated for different types of thermal processes and different types of waste. It emerged that the dominant type of thermal treatment is incineration associated to energy recovery in a steam cycle. When waste gasification is applied, the produced syngas is generally combusted in a boiler to generate steam for energy recovery in a steam cycle. For both the possibilities--incineration or gasification--co-generation is the mean to improve energy recovery, especially for small scale plants. In the case of only electricity production, the achievable values are strongly dependent on the plant size: for large plant size, where advanced technical solutions can be applied and sustained from an economic point of view, net electric efficiency may reach values up to 30-31%. In small-medium plants, net electric efficiency is constrained by scale effect and remains at values around 20-24%. Other types of technical solutions--gasification with syngas use in internally fired devices, pyrolysis and plasma gasification--are less common or studied at pilot or demonstrative scale and, in any case, offer at present similar or lower levels of energy efficiency.

Performance of a biogas upgrading process based on alkali absorption with regeneration using air pollution control residues.

This work analyzes the performance of an innovative biogas upgrading method, Alkali absorption with Regeneration (AwR) that employs industrial residues and allows to permanently store the separated CO2. This process consists in a first stage in which CO2 is removed from the biogas by means of chemical absorption with KOH or NaOH solutions followed by a second stage in which the spent absorption solution is contacted with waste incineration Air Pollution Control (APC) residues. The latter reaction leads to the regeneration of the alkali reagent in the solution and to the precipitation of calcium carbonate and hence allows to reuse the regenerated solution in the absorption process and to permanently store the separated CO2 in solid form. In addition, the final solid product is characterized by an improved environmental behavior compared to the untreated residues. In this paper the results obtained by AwR tests carried out in purposely designed demonstrative units installed in a landfill site are presented and discussed with the aim of verifying the feasibility of this process at pilot-scale and of identifying the conditions that allow to achieve all of the goals targeted by the proposed treatment. Specifically, the CO2 removal efficiency achieved in the absorption stage, the yield of alkali regeneration and CO2 uptake resulting for the regeneration stage, as well as the leaching behavior of the solid product are analyzed as a function of the type and concentration of the alkali reagent employed for the absorption reaction.

Analysis of energy recovery potential using innovative technologies of waste gasification.

In this paper, two alternative thermo-chemical processes for waste treatment were analysed: high temperature gasification and gasification associated to plasma process. The two processes were analysed from the thermodynamic point of view, trying to reconstruct two simplified models, using appropriate simulation tools and some support data from existing/planned plants, able to predict the energy recovery performances by process application. In order to carry out a comparative analysis, the same waste stream input was considered as input to the two models and the generated results were compared. The performances were compared with those that can be obtained from conventional combustion with energy recovery process by means of steam turbine cycle. Results are reported in terms of energy recovery performance indicators as overall energy efficiency, specific energy production per unit of mass of entering waste, primary energy source savings, specific carbon dioxide production.