Catalytic Epoxidation and Sulfoxidation Activity of a Dioxomolybdenum(VI) Complex Bearing a Chiral Tetradentate Oxazoline Ligand

A dioxomolybdenum(vi) complex bearing a tetradentate anionic N,O oxazoline ligand with four stereocenters has been studied as a catalyst in the liquid-phase epoxidation of 17 different aliphatic and aromatic olefins (including prochiral, racemate or pure enantiomers) using tert-butyl hydroperoxide as the oxidant. Epoxide selectivities of up to 100% and variable epoxide yields (3–100% within 24 h) were obtained. Although the complex generally exhibited low or no chiral induction ability, diastereoselectivity was significant in some cases (in the reaction of limonene, for example). Kinetic studies and recycling tests with the substrates cis-cyclooctene and trans-β-methylstyrene showed that the catalyst is stable and reusable, and recycling is facilitated by immobilization of the complex in a room temperature ionic liquid. Preliminary results show that the complex may have a broad substrate scope, not only for olefin epoxidation, but also for the dehydrogenation of alcohols to carbonyl compounds and the sulfoxidation of sulfides to sulfoxides.     

Formation of metal agglomerates during carbonisation of chromated copper arsenate (CCA) treated wood waste: Comparison between a lab scale and an industrial plant

This paper compares the results obtained by scanning electron microscopy coupled to X-ray analysis (SEM-EDXA) of the solid product after carbonisation of treated wood waste in a lab scale and in an industrial installation. These setups (lab scale and industrial) are characterized by different operating conditions of the carbonisation process. Moreover, the wood waste input to the processes differs significantly. From this study, it is clear that some similarities but also some differences exist between the lab scale study and the study with the industrial Chartherm plant. In both reactors, a metal (and mineral) agglomeration process takes place, even in the case of untreated wood. The agglomerates initially present in the wood input may serve as a seed for the metal agglomeration process during "chartherisation". The industrial setup leads to a broader range of agglomerates' size (0.1-50 microm) and composition (all possible combinations of Cu, Cr, As and wood minerals). Some agglomerates contain the three metals but the major part is a combination of wood minerals and one or two of the three preservative metals, while all agglomerates analysed in the lab scale product contain the three metals. The separate influence of wood input characteristics and process conditions cannot be derived from these experiments, but the observations suggest that the higher the CCA retention in the wood input is, the easier is the metal agglomeration process during chartherisation of CCA treated wood waste. From the analyses performed in this study it seems that copper behaves differently in the sense that it agglomerates easily, but the resulting particles are small (<1 microm).     

Reducing Early Retirement in Europe: Do Working Conditions Matter?

The paper argues that the existing literature, based on the Survey of Health, Ageing and Retirement in Europe (SHARE) data, on how working conditions impact on early retirement preferences/plans is hampered by the fact that the approach adopted to capture individuals’ early retirement plans fails to acknowledge that these preferences/plans are defined by reference to the rules that regulate the entitlement to pension benefits. In doing so, these studies risk overestimating the impact of working conditions on early retirement plans. We put forward a more accurate way of capturing individuals’ early retirement preferences/plans, which consists in using information on the age at which respondents plan to start collecting the basic pension benefits, and then computing whether the respondent plans to retire before the official age of retirement in his country of residence. Using SHARE microdata, wave 4, we show that individuals exposed to an imbalance between effort and rewards at work (Siegriest Journal Journal of Occupational Health Psychology, 1(1), 27–41, 1996 ) are more likely to plan to take-up early retirement. We also show that the effect of poor working conditions is smaller than one would find using the previous approach to the measurement of early retirement preferences/plans.     

CFD as an approach to understand flammable dust 20 L standard test: Effect of the ignition time on the fluid flow

A computational study based on the Euler–Lagrange approach was developed for the characterization of flammable dusts in the 20 L sphere standard test. The aim of the study was to analyze some parameters that might affect the experimental data (e.g., cold turbulence and particle size). The turbulence of a wheat starch cloud was described with the Detached Eddy Simulation model. Both the pressure of the system and the RMS velocity were compared with the flow patterns established with a particle image velocimetry analysis. It was concluded that the rebound nozzle forms a cloud that is composed by clumps. This fact implies dissimilarities between the local concentrations and the nominal value. Finally, a granulometric analysis established that the mean diameter of the particle size distribution (PSD) decreased by 69% during the dispersion. Thus, it is suggested to consider the PSD at the ignition zone rather than the PSD of the sample. © 2017 American Institute of Chemical Engineers AIChE J, 63: 42–54, 2018     

Evaluation of solar photo-Fenton parameters on the pre-oxidation of leachates from a sanitary landfill

The main purpose of this work is to study the treatment of a leachate after preliminary aerated lagooning by a solar photo-Fenton process, using a photocatalytic reactor with compound parabolic collectors (CPCs). The influence of different process parameters in the reaction rate was evaluated, such as, the type of acid used in the acidification step (H₂SO₄, HCl, H₂SO₄ + HCl); type of iron salt (FeSO₄, FeCl₃) and respective iron concentration (60, 80, 100 and 140 mg Fe²⁺/L); temperature; and ratio of illuminated to total volume (25 L/35 L; 25 L/72 L). DOC abatement in the acidification procedure is independent of the type of acid used and temperature, and is related principally with the precipitation of humic acids. The use of HCl alone or in combination with H₂SO₄ leads to a substantially increase of the chloride ions, leading to the formation of less reactive chloride radicals when compared with sulfate radicals, decreasing the photo-Fenton reaction rate. The use of ferrous ions instead of ferric ions influenced positively the photo-Fenton reaction. Meteorological conditions favoring higher temperature of the leachate enhance the photo-Fenton reaction. Alternating dark and illumination intervals has shown a negligible effect on the illumination time needed to achieve the same mineralization, indicating that the Fenton process that takes place in dark zones is not efficient, even in the degradation of intermediate compounds resulting from the light-enhanced reaction. According to biodegradability tests, the optimum energy dose, necessary to obtain a biodegradable effluent, is 57.4 kJ_UV/L, consuming 120 mM of H₂O₂ and leading to a final DOC of 284 mg/L which corresponds to approximately 66% of mineralization.     

Microbiological risk assessment for personal care products

Regulatory decisions regarding microbiological safety of cosmetics and personal care products are primarily hazard‐based, where the presence of a potential pathogen determines decision‐making. This contrasts with the Food industry where it is a commonplace to use a risk‐based approach for ensuring microbiological safety. A risk‐based approach allows consideration of the degree of exposure to assess unacceptable health risks. As there can be a number of advantages in using a risk‐based approach to safety, this study explores the Codex Alimentarius (Codex) four‐step Microbiological Risk Assessment (MRA) framework frequently used in the Food industry and examines how it can be applied to the safety assessment of personal care products. The hazard identification and hazard characterization steps (one and two) of the Codex MRA framework consider the main microorganisms of concern. These are addressed by reviewing the current industry guidelines for objectionable organisms and analysing reports of contaminated products notified by government agencies over a recent 5‐year period, together with examples of reported outbreaks. Data related to estimation of exposure (step three) are discussed, and examples of possible calculations and references are included. The fourth step, performed by the risk assessor (risk characterization), is specific to each assessment and brings together the information from the first three steps to assess the risk. Although there are very few documented uses of the MRA approach for personal care products, this study illustrates that it is a practicable and sound approach for producing products that are safe by design. It can be helpful in the context of designing products and processes going to market and with setting of microbiological specifications. Additionally, it can be applied reactively to facilitate decision‐making when contaminated products are released on to the marketplace. Currently, the knowledge available may only allow a qualitative or semi‐quantitative rather than fully quantitative risk assessment, but an added benefit is that the disciplined structuring of available knowledge enables clear identification of gaps to target resources and if appropriate, instigate data generation.     

Assessing the impact of performance determinants in complex MTO/ETO supply chains through an extended hybrid modelling approach

In make-to-order (MTO)/engineer-to-order (ETO) business environments multiple customer-oriented projects compete for and share resources through interdependent engineering and production activities. Deep knowledge of critical dimensions that affect performance is key in this context. For this, we propose a set of determinants – workload, complexity, outsourcing, design reuse, project type, and knowledge/experience with technology, that impact performance. These determinants are input to an extended hybrid simulation model using system dynamics (SD), discrete event simulation (DES) and agent-based simulation (ABS) that tackles the needs imposed by activities of very different nature, as the project development and manufacturing/assembly operations. The hybrid model is applied to the case of an advanced manufacturing company. Through Monte Carlo sampling, the influence of different combinations of determinants in the performance variability is assessed. A correlation analysis shows evidence of association between all performance determinants and the project time and cost, while no evidence of association between the design reuse and project type determinants and the manufacturing and assembly time.