Preliminary analysis of compound systems based on high temperature fuel cell, gas turbine and Organic Rankine Cycle

This article presents a novel proposal for complex hybrid systems comprising high temperature fuel cells and thermal engines. In this case, the system is composed by a molten carbonate fuel cell with cascaded hot air turbine and Organic Rankine Cycle (ORC), a layout that is based on subsequent waste heat recovery for additional power production. The work will credit that it is possible to achieve 60% efficiency even if the fuel cell operates at atmospheric pressure.The first part of the analysis focuses on selecting the working fluid of the Organic Rankine Cycle. After a thermodynamic optimisation, toluene turns out to be the most efficient fluid in terms of cycle performance. However, it is also detected that the performance of the heat recovery vapour generator is equally important, what makes R245fa be the most interesting fluid due to its balanced thermal and HRVG efficiencies that yield the highest global bottoming cycle efficiency. When this fluid is employed in the compound system, conservative operating conditions permit achieving 60% global system efficiency, therefore accomplishing the initial objective set up in the work.A simultaneous optimisation of gas turbine (pressure ratio) and ORC (live vapour pressure) is then presented, to check if the previous results are improved or if the fluid of choice must be replaced. Eventually, even if system performance improves for some fluids, it is concluded that (i) R245fa is the most efficient fluid and (ii) the operating conditions considered in the previous analysis are still valid.The work concludes with an assessment about safety-related aspects of using hydrocarbons in the system. Flammability is studied, showing that R245fa is the most interesting fluid also in this regard due to its inert behaviour, as opposed to the other fluids under consideration all of which are highly flammable.     

Electrical behaviour,characteristics and properties of anodic aluminium oxide films coloured by nickel electrodeposition

Porous anodic films on 1050 aluminium substrate were coloured by AC electrodeposition of nickel. Several experiments were performed at different deposition voltages and nickel concentrations in the electrolyte in order to correlate the applied electrical power to the electrical behaviour, as well as the characteristics and properties of the coatings. The content of nickel inside the coatings reached 1.67 g/m², depending on the experimental conditions. According to the applied AC voltage in comparison with the threshold voltage U _t, the coating either acted only as a capacitor when U < U _t and, when U > U _t, the behaviour during the anodic and cathodic parts of the power sine wave was different. In particular, due to the semi-conducting characteristics of the barrier layer, additional oxidation of the aluminium substrate occurred during the anodic part of the electrical signal, whilst metal deposition (and solvent reduction) occurred during the cathodic part; these mechanisms correspond to the blocked and pass directions of the barrier layer/electrolyte junction, respectively.     

Composite Compressibility Model for Municipal Solid Waste

Three important mechanisms that contribute to the compression of municipal solid waste are instantaneous compression in response to applied load, secondary mechanical creep, and time-dependent biological decomposition. A composite compressibility model that explicitly takes these mechanisms into account was developed and implemented in a computer program to calculate landfill settlements. The model performance was assessed using data from the Bandeirantes Landfill, which is a well-documented landfill located in Sao Paulo, Brazil, and upon which an instrumented test fill was constructed. Model parameter values were obtained by nonlinear regression analysis, and it was found that the composite model tracked observed patterns of landfill settlement very well. Furthermore, the average parameter values from nonlinear regression analyses for 20 instruments exhibited small deviations between calculated and observed settlements, indicating that a single set of parameter values can provide reasonably good representation of all the waste in the vicinity of the test fill. Recommendations for applying the model to other landfills are provided.     

Biodegradability enhancement of a pesticide-containing bio-treated wastewater using a solar photo-Fenton treatment step followed by a biological oxidation process

This work proposes an efficient combined treatment for the decontamination of a pesticide-containing wastewater resulting from phytopharmaceutical plastic containers washing, presenting a moderate organic load (COD = 1662-1960 mg O₂ L⁻¹; DOC = 513-696 mg C L⁻¹), with a high biodegradable organic carbon fraction (81%; BOD₅ = 1350-1600 mg O₂ L⁻¹) and a remaining recalcitrant organic carbon mainly due to pesticides. Nineteen pesticides were quantified by LC-MS/MS at concentrations between 0.02 and 45 mg L⁻¹ (14-19% of DOC). The decontamination strategy involved a sequential three-step treatment: (a) biological oxidation process, leading to almost complete removal of the biodegradable organic carbon fraction; (b) solar photo-Fenton process using CPCs, enhancing the bio-treated wastewater biodegradability, mainly due to pesticides degradation into low-molecular-weight carboxylate anions; (c) and a final polishing step to remove the residual biodegradable organic carbon, using a biological oxidation process. Treatment performance was evaluated in terms of mineralization degree (DOC), pesticides content (LC-MS/MS), inorganic ions and low-molecular-weight carboxylate anions (IC) concentrations. The estimated phototreatment energy necessary to reach a biodegradable wastewater, considering pesticides and low-molecular-weight carboxylate anions concentrations, Zahn-Wellens test and BOD₅/COD ratio, was only 2.3 kJ_UV L⁻¹ (45 min of photo-Fenton at a constant solar UV power of 30 W m⁻²), consuming 16 mM of H₂O₂, which pointed to 52% mineralization and an abatement higher than 86% for 18 pesticides. The biological oxidation/solar photo-Fenton/biological oxidation treatment system achieved pesticide removals below the respective detection limits and 79% mineralization, leading to a COD value lower than 150 mg O₂ L⁻¹, which is in agreement with Portuguese discharge limits regarding water bodies.     

Électrodes poreuses percolées constituées de métal fritté: Hydrodynamique et transfert de matière

Percolated porous electrodes made of commercial sintered nickel were stuided for different configurations (percolated sheet; radially percolated tube wall; porous tube with simultaneous axial and percolated radial flows). The materials were characterized using permeametry experiments, and the volumetric mass transfer coefficients were electrochemically measured. Empirical correlations of the results were obtained for the case of one-dimensional electrodes (axial and radial electrodes); they were compared with other correlatinos from the literature. The results obtained for the case of combined axial and aspiration flows are discussed.     

Turning Laminaria digitata seaweed into a resource for sustainable and ecological removal of trivalent chromium ions from aqueous solutions

This study presents the application of a safe, cost effective, environmental friendly, and efficient technology for the removal of trivalent chromium ions from aqueous solutions, based on the valorisation of a renewable resource, Laminaria digitata seaweed. Insights into trivalent chromium speciation in solution and interaction with the active sites present in the surface of the brown algae were studied. Carboxyl and hydroxyl groups were identified as the major binding sites present in the surface of the biosorbent, in concentrations (Q _max) of 2.06 ± 0.01 and 1.4 ± 0.7 mmol g^?1, and with proton binding parameters (pK) of 3.28 ± 0.01 and 11 ± 1, respectively. Trivalent chromium uptake at equilibrium conditions was well described at different acidic pH conditions and chromium concentrations, using a model which incorporates trivalent chromium hydrolysis reactions in the aqueous phase and its chemical interactions with the available active sites (carboxyl groups) present in the surface of biosorbent. The distribution profile of trivalent chromium species present in the solution as well as at the binding sites indicated that Cr³⁺ and CrOH²⁺ exhibit different affinities for the carboxyl groups present in the surface of the biomass according to the pH. A mass transfer kinetics model was applied to describe the kinetics at batch system, being possible to obtain the distribution of CrOH²⁺ and Cr³⁺ species in solution and at the binding sites.     

β-cyclodextrin as inverse phase transfer catalyst on the electrocatalytic hydrogenation of organic compounds in water

The optimum conditions for the electrocatalytic hydrogenation (ECH) of benzaldehyde in water, using a nickel sacrificial anode (SA) (referred to as ECH-SA) and β-cyclodextrin (β-CyD) as inverse phase transfer catalyst (IPTC) were determined. Four parameters were investigated: the morphology of the nickel deposited on the cathode matrix (Cu, Fe, Ni or Fe/Ni alloy (64:36)) during a pre-electrolysis, the size of the CyD cavity, the concentration of β-CyD, the supporting electrolyte concentration and the current density applied. The results showed that a Ni matrix together with ultrasound pre-electrolysis treatment allowed a nanostructured nickel deposit on the cathode surface. Under the best electrolysis conditions (2.8 mmol dm^?3 of β-CyD, 1.0 mol dm^?3 of NH₄Cl and a current density of 330 mA dm^?2), the yield of benzyl alcohol (99%) was 27% higher than that obtained under the same conditions but in the absence of β-CyD. Taking into account the hydrophobic character of the β-CyD, the best conditions of the ECH-SA method were applied to the hydrogenation of a variety of organic substrates. Excellent yields and current efficiencies were obtained with arylbenzaldehydes and acetophenone. ECH-SA of styrene gave moderate yield and current efficiency, and the hydrogenation of a terminal non-conjugated olefin (safrole) was not efficient.     

Electrodeposition of gold thin films from 1-butyl-1-methylpyrrolidinium dicyanamide Au solutions

The electrodeposition of gold from a HAuCl₄.3H₂O solution in 1-butyl-1-methyl-pyrrolidinium dicyanamide is reported in the present paper. A cyclic voltammetry study of the electrochemical behaviour of the plating solution showed that the reduction of gold occurs by a two-step process. Gold thin films were obtained by electrodeposition on nickel substrates under potentiostatic control at a constant potential of − 1 V, for temperatures from 293 to 353 K and deposition times of 1500 and 4500 s. The films prepared at 293 and 333 K consist of 9-15 nm diameter polyhedral particles aggregated in clusters 50-250 nm in diameter. The films deposited at 353 K consist of a quasi-continuous film of nanoparticles covered by nanosized dendrites. This morphology evolves towards a globular structure with increasing deposition time.