Effect of olive paste kneading process time on the overall quality of virgin olive oil

The influence of the olive paste malaxation time on the composition and the industrial output of oil was investigated. To this purpose, three Italian olive varieties (Leccino, Dritta, Caroleo) were processed with a centrifugal system for six malaxation periods (0, 15, 30, 45, 60 and 75 min). The concentrations of the majority of the oil constituents changed during the malaxation. However, these changes were not significant for all of them: the contents of β‐carotene, the major xanthophylls, chlorophylls a and b, pheophytins a and b in the oils increased progressively with increasing malaxing times, whereas the contents of simple and hydrolysable phenols (secoiridoid derivatives), o‐diphenols and total phenols decreased. A significant increase in total volatiles and green volatiles of the lipoxygenase cascade (C₆ aldehydes, C₆ alcohols, C₅ alcohols and C₅ carbonyls) was detected. An opposite trend was observed for the green C₆ esters. As a result, the global analytical quality, flavour, aroma and shelf‐life of the oils were negatively affected. The oil yield increased substantially up to 45 min of paste malaxation times. Beyond 60 min, the yields tended to decrease.     

Ultrahigh temperature water gas shift catalysts to increase hydrogen yield from biomass gasification

Noble metal (Rh, Pt, Pd, Ir, Ru, and Ag) and Ni catalysts supported on CeO₂–Al₂O₃ were investigated for water gas shift reaction at ultrahigh temperatures. Pt/CeO₂–Al₂O₃ and Ru/CeO₂–Al₂O₃ demonstrated as the best catalysts in terms of activity, hydrogen yield and hydrogen selectivity. At 700 °C and steam to CO ratio of 5.2:1, Pt/CeO₂–Al₂O₃ converted 76.3% of CO with 94.7% of hydrogen selectivity. At the same conditions, the activity and hydrogen selectivity for Ru/CeO₂–Al₂O₃ were 63.9% and 85.6%, respectively. Both catalysts showed a good stability over 9 h of continuous operation. However, both catalysts showed slight deactivation during the test period. The study revealed that Pt/CeO₂–Al₂O₃ and Ru/CeO₂–Al₂O₃ were excellent ultrahigh temperature water gas shift catalysts, which can be coupled with biomass gasification in a downstream reactor.     

Catalytic combustion of trichloroethene over Ru/Al2O3: Reaction mechanism and kinetic study

The performance of 0.5% Ru/Al₂O₃ for the deep oxidation of trichloroethene (1000–2500 ppmV, WHSV = 55 h⁻¹) in air was studied in this work. Experiments were carried out both at dry and wet (20,000 ppmV of H₂O) conditions. Catalytic performance was studied in terms of activity and selectivity for the different reaction products (CO₂, HCl, Cl₂, C₂Cl₄, CCl₄ and CHCl₃). Both the activity and the selectivity for total combustion are higher than other catalysts suggested in the literature for this process (especially Pd and Pt).The main organic by-products are CCl₄ and CHCl₃, whereas in all the other catalysts tested in the literature, tetrachloroethene is the main organic by-product. This fact suggests that the mechanism of the combustion reaction, involving a double-bond scission, is essentially specific for this catalyst.Kinetic data was fit to a pseudo-first order kinetic expression, providing fairly good fit.     

A study about the effect of the temperature of hydrogen treatment on the properties of Ru/Al2O3 and Ru/C and their catalytic behavior during 1-heptyne semi-hydrogenation

The 1-heptyne selective hydrogenation carried out at 150 kPa, and at 283 and 303 K using Ru/Al₂O₃ and Ru/C as catalysts, was studied. Catalysts were prepared by the incipient wetness impregnation technique using RuCl₃ as precursor. Ru/Al₂O₃ was treated in hydrogen at 373 or 573 K and Ru/C only at the last temperature. Catalysts were characterized by hydrogen chemisorption, TPR and XPS. Ru dispersion after treatment in hydrogen at the highest temperature is similar for both catalysts. Ru is present as Ru⁰ in Ru/C, while Ru⁰ and Ru electron-deficient species are present on the catalysts surface after hydrogen treatment at the two temperatures using Al₂O₃ as support. The best catalytic behavior was observed for the highest temperature of hydrogen treatment and for 303 K reaction temperature. As a consequence of a shape selectivity effect of the C support, the best conversion is obtained with the alumina supported catalyst.     

Theory of asymmetric organocatalysis of Aldol and related reactions: rationalizations and predictions

Computational studies have led to models to understand some classic and contemporary asymmetric reactions involving organocatalysts. The Hajos-Parrish-Eder-Sauer-Wiechert reaction and intermolecular aldol reactions as well as Mannich reactions and oxyaminations catalyzed by proline and other amino acids, and Diels-Alder reactions catalyzed by MacMillan's chiral amine organocatalysts have been studied with density functional theory. Quantitative predictions for several new catalysts and reactions are provided.     

Designing biomass supply chains within planetary boundaries

The design of sustainable supply chains, which recently emerged as an active area of research in process systems engineering, is vital to ensure sustainable development. Despite past and ongoing efforts, the available methods often overlook impacts beyond climate change or incorporate them via standard life cycle assessment metrics that are hard to interpret from an absolute sustainability viewpoint. We here address the design of biomass supply chains considering critical ecological limits of the Earth—planetary boundaries—which should never be surpassed by anthropogenic activities. Our method relies on a mixed-integer linear program that incorporates a planetary boundaries-based damage model to quantify absolute sustainability precisely. We apply this approach to the sugarcane-to-ethanol industry in Argentina, identifying the optimal combination of technologies and network layout that minimize the impact on these ecological boundaries. Our framework can find applications in a wide range of supply chain problems related to chemicals and fuels production, energy systems, and agriculture planning.     

Mechanochemical tuning of molecular weight distribution of styrene homopolymers as postpolymerization modification in solvent-free solid-state

Mechanochemical degradation by planetary ball milling (PM) is used for postpolymerization modification of styrene homopolymers (PS). A complete factorial design was chosen to study the effect of radical scavengers, milling time, initial molecular weight, and revolution radius (R_p), on the shape of molecular weight distributions (MWDs) of PS. Size-exclusion chromatography analysis shows the feasibility of fine-tuning MWD of PS at up to 40% conversion. Distributions ranged from unimodal to bimodal in a PM with R_p = 150 mm at different stage of milling, whereas in a PM with R_p of 60.8 mm the adjustment of unimodal distributions is achieved. Initial polydispersity is more important to develop bimodal distributions when compared with initial molecular weight. Fourier transform infrared and X-ray electron spectrometry analysis show some suppression of PS degradation and complete oxidation inhibition of macromolecular radicals with the incorporation of radical scavengers, which we considered as additional aids when adjusting the MWDs.     

Modelling and analysis of non-cooperative peer-assisted VoD streaming in managed networks

The growing popularity of the Video on Demand service in the Internet Protocol Television environments and the demand for increased quality of the offered videos are becoming a serious threat for the service providers because the high amounts of video traffic are causing congestion in the delivery networks. One of the most acceptable approaches to solve this issue is the peer-assisted streaming, where the peers participate in the streaming process in order to alleviate the load on the streaming servers and in the core of the network. Although the reliability of the Peer-to-Peer service is considerably improved in the managed networks because of the control that the operators have over the clients’ Set-Top Boxes, the failures of the peers still cannot be completely eliminated. The operator can take advantage of the streaming and storage resources of the clients and use them for peer-assisted streaming only while they are watching a video, but not after they finish the streaming session because they may turn off their receiving devices until the next session. In this chapter, we address the issue of the failures of the peers in such environments and their influence on the traffic requested from the servers for providing uninterrupted video experience. For that purpose, we propose a precise mathematical tool for modelling a peer-assisted system for Video on Demand streaming in managed networks with non-cooperative peers, which may decide not to share their resources while they are not active. This tool calculates the performance of the system taking into consideration large variety of system parameters, including the failure probability and the time the peers spend until they decide to turn on the STB and join the network. As the results from the simulations verify the correctness of the mathematical model, we use it to analyse how the failures of the peers are affecting the system’s performance for different system parameters.