Effects of carbonate on the electrolytic removal of ammonia and urea from urine with thermally prepared IrO<Subscript>2</Subscript> electrodes

Recent studies have shown that electrolysis can be an efficient process for nitrogen removal from urine. These studies have been conducted with urea solutions or fresh urine, but urine collected in NoMix toilets and urinals has a substantially different composition, because bacteria hydrolyse urea quickly to ammonia and carbonate. In this study, we compared electrochemical removal of nitrogen from synthetic solutions of fresh and stored urine using IrO₂ anodes. We could show that in fresh urine both ammonia and urea are efficiently eliminated, mainly through chlorine-mediated oxidation. However, in stored urine the presence of carbonate, arising from urea hydrolysis, leads to an inhibition of ammonia oxidation. We suggest two parallel mechanisms to explain this effect: the competition between chloride and carbonate oxidation at the anode and the competition between chlorate formation, enhanced by the buffering effect of carbonate, and ammonia oxidation for the consumption of active chlorine in the bulk. However, further experiments are needed to support the latter mechanism. In conclusion, this study highlights the negative consequences of the presence of carbonate in urine solutions, but also in other wastewaters, when subjected to an electrolytic treatment on IrO₂ in alkaline media.     

Electrochemical destruction of chlorophenoxy herbicides by anodic oxidation and electro-Fenton using a boron-doped diamond electrode

The degradation of herbicides 4-chlorophenoxyacetic acid (4-CPA), 4-chloro-2-methylphenoxyacetic acid (MCPA), 2,4-dichlorophenoxyacetic acid (2,4-D) and 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) in aqueous medium of pH 3.0 has been comparatively studied by anodic oxidation and electro-Fenton using a boron-doped diamond (BDD) anode. All solutions are totally mineralized by electro-Fenton, even at low current, being the process more efficient with 1 mM Fe²⁺ as catalyst. This is due to the production of large amounts of oxidant hydroxyl radical (OH) on the BDD surface by water oxidation and from Fenton’s reaction between added Fe²⁺ and H₂O₂ electrogenerated at the O₂-diffusion cathode. The herbicide solutions are also completely depolluted by anodic oxidation. Although a quicker degradation is found at the first stages of electro-Fenton, similar times are required for achieving overall mineralization in both methods. The decay kinetics of all herbicides always follows a pseudo first-order reaction. Reversed-phase chromatography allows detecting 4-chlorophenol, 4-chloro-o-cresol, 2,4-dichlorophenol and 2,4,5-trichlorophenol as primary aromatic intermediates of 4-CPA, MCPA, 2,4-D and 2,4,5-T, respectively. Dechlorination of these products gives Cl⁻, which is slowly oxidized on BDD. Ion-exclusion chromatography reveals the presence of persistent oxalic acid in electro-Fenton by formation of Fe³⁺-oxalato complexes, which are slowly destroyed by OH adsorbed on BDD. In anodic oxidation, oxalic acid is mineralized practically at the same rate as generated.     

Cyclic cold isostatic pressing and improved particle packing of coarse grained oxide ceramics for refractory applications

This study investigated the cold isostatic pressing of coarse grained alumina refractories applying either a cyclic pressure increase or a cycling at maximum pressure. Additionally the effects of the maximum pressure and the particle size distribution on physical, mechanical and thermomechanical properties were analyzed. The cyclic pressure increase resulted in a slightly higher apparent density and lower apparent porosity. A cycling at maximum pressure decreased the median pore size to some extent. Remarkably, an optimized particle size distribution resulted in a lower apparent porosity, lower median pore size and in a higher Young's modulus before and after thermal shock together with a slightly lower relative decrease of the Young's modulus. A higher pressing pressure which decreased the apparent porosity did not affect the Young's modulus. Thus, apparently the optimized particle size distribution improved the particle packing which was associated with a smaller median pore size. This smaller pore size increased the number of pores relative to the total porosity, which then acted as points of crack initiation and crack deflection limiting the length of propagating cracks in case of thermal shock. Thus, tailoring the pore size distribution is a promising starting point to improve the thermomechanical properties of refractories.     

Steam‐air blown bubbling fluidized bed biomass gasification (BFBBG): Multi‐scale models and experimental validation

During fluidized bed biomass gasification, complex gas‐solid mixing patterns and numerous chemical and physical phenomena make identification of optimal operating conditions challenging. In this work, a parametric experimental campaign was carried out alongside the development of a coupled reactor network model which successfully integrates the individually validated sub‐models to predict steady‐state reactor performance metrics and outputs. The experiments utilized an integrated gasification system consisting of an externally‐heated, bench‐scale, 4‐in., 5 kWth, fluidized bed steam/air blown gasifier fed with woody biomass equipped with a molecular beam mass spectrometer to directly measure tar species. The operating temperature (750–850°C) and air/fuel equivalence ratio (ER = 0–0.157) were independently varied to isolate their effects. Elevating temperature is shown to improve the char gasification rate and reduce tar concentrations. Air strongly impacts the composition of tar, accelerating the conversion of lighter polycyclic‐aromatic hydrocarbons into soot precursors, while also improving the overall carbon conversion. © 2016 American Institute of Chemical Engineers AIChE J, 63: 1543–1565, 2017     

Passive Filtration of Airborne Particles from Buildings Ventilated by Natural Convection: Design Procedures and a Case Study at the Buddhist Cave Temples at Yungang,China

Air exchange between interior spaces and the outdoor atmosphere can occur due to a variety of processes, including wind-driven flows and natural convectiondriven flows. As air is exchanged with the outdoors, airborne particles can be brought inside. Depending on the use of the indoor space, the presence of particles in indoor air could be a nuisance to the occupants or could be damaging to materials kept indoors. While one obvious solution to such problems is to install a mechanical air filtration system, that is not always practical. In particular, the character of some historical houses and some archaeological sites would be degraded by the presence of a mechanical air distribution system, and in some parts of the world the reliable electrical power supply needed for such a filtration system may not be available. In the present paper we consider principles for the design of passive filtration systems in which air motion through the filter material is induced by a natural convection flow rather than by a mechanical fan. A fluid mechanical model first is described for predicting the air flow through an interior space that acts as a thermal siphon. The effect of placing filter material in the path of such air flows is examined next. The indoor-outdoor air quality model of Nazaroff and Cass (1989a) is matched to the natural convection air exchange model, and calculations are performed to determine the relationship between the outdoor particle size distribution and indoor particle size distributions and particle deposition rates given a passive filtration system. Example calculations are worked for the case of a passive particle filtration system that could be installed to protect the interior of the Buddhist cave temples at Yungang, China. These are a collection of manmade cave temples dating from the 5th century AD, now situated in the middle of one of China's largest coal-mining regions with its accompanying air pollution problems.     

Synthesis, optical and morphological characterization of soluble main chain 1,3,4-oxadiazole copolyarylethers—potential candidates for solar cells applications as electron acceptors

New copoly(arylether)s containing substituted terphenyl, quinquephenyl, fluorene and anthracene moieties with aromatic 1,3,4-oxadiazole units were prepared and the resulting copolymers are soluble in common organic solvents. Investigation of their optical properties revealed that they emit blue and yellow light. Moreover, their photovoltaic response was studied in blends with poly(3-hexylthiophene) (P3HT) as the electron donor. Despite the low power conversion efficiencies it was shown that photo-induced electron transfer does take place and the performances are higher than a single layer P3HT device. In addition, an anthracene-fluorene-oxadiazole main chain copolymer (PAFOXD) was also examined in a single layer photovoltaic device and gave one of the highest reported open-circuit voltage (V_oc) values in the literature (0.89 V). Finally, a detailed morphological study of the blends and the PAFOXD surface using the atomic force microscopy (AFM) technique, revealed the effect of solvent selection to the preparation of thin films exhibiting the desired performance characteristics.     

Electrochemical comparison of IrO2 prepared by anodic oxidation of pure iridium and IrO2 prepared by thermal decomposition of H2IrCl6 precursor solution

Surface redox activities, oxygen evolution reaction (OER), oxidation of formic acid (FA), and anodic stability were investigated and compared for IrO₂ electrodes prepared by two techniques: the thermal decomposition of H₂IrCl₆ precursor (TDIROF) and the anodic oxidation of metallic iridium (AIROF). Surface redox activities involved on the AIROF were found to be much faster than those involved on the TDIROF. Concerning the oxygen evolution reaction, both films show a similar mechanism and specific electrocatalytic activities. The situation seems to be different for FA oxidation. In fact, on TDIROF, the oxidation of FA and the OER compete involving the same surface redox couple Ir(VI)/Ir(IV) contrary to FA oxidation on AIROF, where the Ir(V)/Ir(IV) surface redox couple is involved. Finally, electrode stability measurements have shown that contrary to TDIROF, which are very stable under anodic polarization, the AIROF are rapidly corroded under anodic treatment. This corrosion is enhanced even further in the presence of formic acid.     

A comparative study on the electrical and mechanical behaviour of multi‐walled carbon nanotube composites prepared by diluting a masterbatch with various types of polypropylenes

Polypropylene (PP) nanocomposites with multi‐walled carbon nanotubes (CNT) were produced by a small‐scale masterbatch melt dilution technique using five PP differing in melt flow index (MFI) and degree of maleination. PP used in a masterbatch has MFI = 12 (PP₁₂), the others used PP which have MFI = 2 or MFI = 8. The state of CNT dispersion as assessed by melt rheological and morphological investigations indicated a better dispersion when using unmodified PP with MFI = 8 (PP₈) and the masterbatch's PP₁₂. Electrical conductivity results showed nanotube percolation at contents between 1.1 and 2.0 vol %, whereas lower values were obtained for the matrices with the best dispersion, i.e., PP₈ and PP₁₂. The dependencies of the relative Young's modulus on the CNT content showed that the maleinization improved the interfacial interactions between the components, especially in the case of maleated PP with MFI = 8 (PP‐MA₈), but the better dispersion was prevented by the incompatibility between polar groups of PP‐MA and the nonpolar origin masterbatch PP₁₂. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009