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     

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 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     

A stochastic programming approach for clinical trial planning in new drug development

The paper presents a multi-stage stochastic programming formulation for the planning of clinical trials in the pharmaceutical research and development (R&D) pipeline. Scenarios are used to account for the endogenous uncertainty in clinical trial outcomes. Given a portfolio of potential drugs and limited resources, the model determines the trials to be performed in each planning period and scenario. To reduce the size of the formulation we employ a reduced set of scenarios without compromising the quality of uncertainty representation. Furthermore, we present a number of ideas that allow us to reduce the number of non-anticipativity constraints necessary to model indistinguishable scenarios. The proposed approach is the first stochastic programming formulation to address this problem.     

Development of [60] fullerene supported on silica catalysts for the photo-oxidation of alkenes

Simple or successive incipient wetness impregnation followed by heating at 180 °C is proved an efficient preparation method for dispersing effectively onto the silica surface various amounts of C₆₀ in the range 1–4% (w/w). BET, XRD, DRS, TGA, microelectrophoresis and photoluminescence have been used to characterize the photocatalysts prepared. A high dispersion was obtained for the quite stable supported C₆₀ phase, comprised mainly from relatively small or medium size C₆₀ clusters/aggregates. The photocatalytic activity was assessed in the singlet oxygen oxidation of alkenes by examining the photo-oxygenation of 2-methyl-2-heptene as a probe reaction. The catalytic tests were carried out at 0–5 °C in CH₃CN, under oxygen atmosphere and using a 300 W xenon lamp as the light source. The heterogeneous catalysts obtained were proved to be active in the photocatalytic oxidation of olefins via a ¹O₂ ene reaction. The catalysts exhibited significant conversion, turnover number and turnover frequency values, substantially higher than those achieved over the unsupported C₆₀. The conversion increases with the amount of the supported C₆₀ up to a value equal to 3% (w/w) and then it decreases whereas turnover number and turnover frequency decreases monotonically as the amount of the supported C₆₀ increases. The easy separation of these solid catalysts from the reaction mixture, the high activity and stability as well as the retained activity in subsequent catalytic cycles, make these supported catalysts suitable for a small-scale synthesis of fine chemicals.     

Determination of azinphos-methyl and parathion-methyl in honey by stripping voltammetry

An electrochemical method for the determination of azinphos-methyl and parathion-methyl in honey is presented. The determination is established by adsorptive stripping differential pulse voltammetry at hanging mercury working electrode.In contrast to the chromatographic methods for the determination of pesticide residues, the sample preparation of the proposed method is minimal; analytes were extracted from honey samples with a mixture of (acetone):(Britton-Robinson buffer) and then were analyzed without any additional pretreatment.The response of the analytes either individually or as a mixture was studied for a series of deposition time and molar ratio. Two quantitation protocols were compared, using either the external calibration or the standard addition method. Accuracy was tested with spiked honey samples obtaining good recovery values. The limit of detection for the honey sample (for deposition time of 10 s) was calculated 51.71 μg kg⁻¹ for MeP and 65.87 μg kg⁻¹ for AzMet.     

Superparamagnetic polyvinylpyrrolidone/chitosan/Fe3O4 electrospun nanofibers as effective U(VI) adsorbents

Magnetoactive electrospun fibrous membranes consisting of polyvinylpyrrolidone (PVP), chitosan (CS) and pre-fabricated, double-layer oleic acid-coated magnetite nanoparticles (OA.OA.Fe₃O₄) were fabricated and evaluated as new adsorbent materials for the removal and recovery of uranium (U(VI)) from aqueous solutions. The adsorption has been investigated by batch-type experiments and the solid material has been characterized by X-ray diffraction spectroscopy (XRD), Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscopy/energy dispersive X-ray analysis (TEM/EDX) and vibration sample magnetometry (VSM) measurements prior and after uranium adsorption. The experimental adsorption data were found to be well fitted with the Langmuir isotherm and the pseudo-second order kinetic model. The results indicate that PVP/CS/OA.OA.Fe₃O₄ fibrous adsorbents exhibit good adsorption properties towards U(VI) in aqueous solutions, achieving a q_max value of 0.77 mol kg⁻¹ (183.3 mg g⁻¹) at pH 6.0. The experiments regarding the regeneration and reuse of the magnetoactive adsorbents were carried out using Na₂CO₃, at pH ~11. After four cycles, the percentage relative adsorption remained stable (~100%) whereas the desorption percentage decreased from 31.9% to 21.0%. Generally, the presented results demonstrate that the incorporation of the Fe₃O₄ NPs has a positive effect on the adsorption efficiency of U(VI) from aquatic environments.     

A general framework and optimization models for the scheduling of continuous chemical processes

We present a framework for the formulation and solution of continuous process scheduling problems. We focus on modeling transient operations such as startups, shutdowns, and transitions between steady states. First, we show how the concept of processing tasks can be generalized to represent continuous processes, including their transient operations. Second, we discuss how to systematically calculate the parameters describing material consumption/production and utility consumption during transient operations. Finally, we present new mixed-integer linear programming formulations for the scheduling of continuous chemical production.