Oxidative dehydrogenation of butenes over Bi‐Mo and Mo‐V based catalysts in a two‐zone fluidized bed reactor

The oxidative dehydrogenation of a 1‐butene/trans‐butene (1:1) mixture to 1,3‐butadiene was carried out in a two‐zone fluidized bed reactor using a Mo‐V‐MgO and a γ‐Bi₂MoO₆ catalyst. The significant operating conditions temperature, oxygen/butene molar ratio, butene inlet height, and flow velocity were varied to gain high 1,3‐butadiene selectivity and yield. Furthermore, axial concentration profiles were measured inside the fluidized bed to gain insight into the reaction network in the two zones. For optimized conditions and with a suitable catalyst, the two‐zone fluidized bed reactor makes catalyst regeneration and catalytic reaction possible in a single vessel. In the lower part of the fluidized bed, the oxidation of coke deposits on the catalyst as well as the filling of oxygen vacancies in the lattice can occur. The oxidative dehydrogenation reaction takes place in the upper zone. Thorough particle mixing inside fluidized beds causes permanent particle exchange between both zones. © 2016 American Institute of Chemical Engineers AIChE J, 63: 43–50, 2017     

Imaging of Extracellular pH Using Hyperpolarized Molecules

Many diseases can overrule natural pH regulatory mechanisms and alter the extracellular pH (pH_e). A non-invasive method that resolves pH_e in vivo with high spatial and temporal resolution could therefore improve diagnosis and monitoring of diseases, contributing to the concept of precision medicine. During the last decades, several techniques have been proposed to image pH_e non-invasively. The majority of these methods rely on magnetic resonance because of its good spatial resolution, high penetration depth, non-ionizing radiation and excellent complimentary soft tissue contrast. Dissolution dynamic nuclear polarization (DNP) is an emerging concept to enhance nuclear magnetic resonance (NMR) signals by more than four orders of magnitude, making it possible to observe in vivo metabolic processes in real-time. Here, we summarize and review recent developments in pH_e imaging techniques based on hyperpolarization methods and give an overview of recently discovered hyperpolarized pH sensor molecules that have been applied in vitro and in vivo.     

Sludge Pre-Treatment through Ozone Application: Alternative Sludge Reuse Possibilities for Recirculating Aquaculture System Optimization

Recirculating Aquaculture Systems (RAS) reduce water consumption by efficient filtration to maintain appropriate levels of accumulating compounds and sludge. Sludge is mechanically separated by drum filters and disposed of to the detriment of overall system water budgets. Dissolved nitrogen compounds are reduced via nitrification–denitrification filters, requiring commercial external carbon sources. The reuse of sludge after ozone pre-treatment may represent the next step in RAS optimization. The present study analyzes the content of sludge from RAS and tests ozonation as a pre-treatment for recycling as carbon source. The dissociative effect of ozone and the physicochemical changes due to ozonation lead to a significant increase in soluble carbon availability. Predominantly long-chain fatty acid (FA) (saturated and unsaturated) with 16 and 18 carbon atoms independently of the treatment were found in the profiles. Saturated FA concentrations in solution increased after 20, 40, and 60 min ozonation. The solid content of the sludge was practically unaffected by ozonation in terms of FA profile: only saturated FA slightly increases after 40 min treatment. The implications of these findings for denitrifying bacteria are discussed.

Abbreviations: Recirculating Aquaculture Systems (RAS); Advanced Oxidation Processes (AOPs)     

Modeling the effect of a superabsorbent polymer material as desiccant in maize drying using CFD

Maize is an important foodstuff in many countries, and one of most susceptible crops to mold and aflatoxin contamination, which results in considerable postharvest losses and is a burden to consumers’ health, especially in developing countries. The timely drying of harvested maize is essential to halt mold development, ensuring safe storage. The effect of the incorporation of a superabsorbent polymer (SAP) as desiccant in a maize dryer was studied using computational fluid dynamics simulations which accounted for heat and mass transfer between maize, SAP and air. The adsorption capacity and adsorption rate of a commercial SAP material were experimentally determined at different temperature and relative humidity levels, which served as basis for the adsorption model required in the simulations. A maize bulk with SAP packages distributed in it was modeled. Results showed that the SAP material increases the drying rate substantially, particularly in the upper bulk zone where the air reaching it is dehumidified the most. The maize closer to the upper bulk surface starts drying from the beginning of the process instead of lagging for hours or days before the drying front reaches it. An inconvenience of the SAP material is the tendency of granules to swell and stick together as moisture reaches a threshold, which may reduce its performance. Thus, provided this issue is resolved or minimized, SAP materials could successfully assist the rapid drying of maize and other crops. They may also be used during storage to avoid rewetting of the crops during periods of high relative humidity.     

An agent-based concept for planning and control of the production of carbon fibre reinforced plastics aircraft structures with mobile production units

This article is concerned with the control of the production of aircraft primary structures made of carbon fibre reinforced plastics. To increase the parallelization of the production, a scenario that implies new design paradigms is discussed. In order to realize this parallelization, mobile production entities work concurrently at the same primary structure of the fuselage. The present article proposes a software architecture for the control of such a production system. It is proposed that components are organized hierarchically. In enhancement to previous proposals, two perspectives of hierarchy are used here: grouping by functionality and grouping by timing context. The core of the architecture is a market-based multi-agent system, where the agents may operate in multiple timing contexts. Such a design yields advantages in terms of fast integration of new functionalities and scale-up of the production system. In brief, this article introduces a top-level control architecture for parallelized production of large reliable CFRP structures in a scalable production system.     

Structure-property relations in ZrCN coatings for tribological applications

ZrCN coatings were deposited by dc reactive magnetron sputtering with N₂ flows ranging from 2 to 10 sccm in order to investigate the influence of the nitrogen incorporation on structure and properties. Information about the chemical composition was obtained by glow discharge optical emission spectroscopy and Rutherford backscattering spectroscopy. The evolution of the crystal structure studied by X-ray diffraction revealed the formation of a face-centred cubic ZrCN phase for N₂ flows greater than 4 sccm. Additionally, the presence of an amorphous phase in the coatings deposited with the highest N₂ flows could be evidenced by Raman spectroscopy and X-ray photoelectron spectroscopy. This phase can act as a lubricant resulting in a low coefficient of friction as shown in the conducted ball-on-disc tests. Nanoindentation measurements showed that coatings deposited with a 6 sccm N₂ flow had the maximum hardness which also revealed the best performance in the conducted dry cutting tests.     

Structure, mechanical properties and oxidation behaviour of arc-evaporated NbAlN hard coatings

Nb_1 − xAl_xN hard coatings were synthesised by cathodic arc-evaporation in order to study the influence of the Al concentration on crystal structure, mechanical properties and oxidation resistance. Structural investigations by X-ray diffraction revealed a transition from the face-centered cubic structure of δ-NbN to the wurtzite structure of AlN at x = 0.45… 0.56 depending on the deposition parameters. The maximum values of the mechanical properties like hardness and residual stress obtained by nanoindentation and biaxial stress temperature measurements, respectively, were found for the coatings with cubic structure and generally decrease with increasing Al content. On the other hand, higher Al concentrations are beneficial in terms of oxidation resistance as shown by annealing experiments in ambient air. The onset temperature for oxidation rises from 600 to 700 °C for Nb_0.73Al_0.27N to above 800 °C for Nb_0.29Al_0.71N regardless of changes in the crystal structure.     

Sugar fatty acid ester surfactants: Base-catalyzed hydrolysis

Rate constants for the base-catalyzed hydrolysis of sucrose laurate, sucrose α-sulfonyl laurate, and sucrose α-ethyl laurate were measured at several temperatures in pH 11 buffer. Activation energies and Arrhenius factors for the hydrolysis reactions were determined. At 27°C, sucrose laurate hydrolyzed fastest and sucrose α-ethyl laurate slowest. Activation energies and Arrhenius factors showed that both steric and electronic factors affect the rates of ester hydrolysis. Other work has shown that bacterial hydrolysis of sugar fatty acid esters is inhibited in the presence of either α-sulfonyl or α-alkyl groups. A kinetic study of base-catalyzed ester hydrolysis has revealed reasons for the inhibition of bacterial hydrolysis and provided information regarding ester stability at elevated pH.     

Development of reactions of silacyclopropanes as new methods for stereoselective organic synthesis

In this Account, we describe the development of stereospecific, stereoselective, regioselective, and chemoselective carbon-carbon bond-forming reactions of silacyclopropanes that occur under mild conditions. By appropriate choice of metal salt catalyst, the regiochemistry of these reactions may be tuned to give the desired product. Stereoselective nucleophilic substitution reactions and stereospecific oxidation of the C-Si bond to a carbon-oxygen bond demonstrate that the products of these reactions serve as useful intermediates for the synthesis of polyoxygenated organic molecules.     

Sugar fatty acid ester surfactants: Structure and ultimate aerobic biodegradability

Ultimate aerobic biodegradabilities of an array of sugar ester surfactants were determined by International Standards Organisation method 7827, “Water Quality—Evaluation in an Aqueous Medium of the Aerobic Biodegradability of Organic Compounds, Method by Dissolved Organic Carbon” (1984). The surfactants were nonionic sugar esters with different-sized sugar head groups (formed from glucose, sucrose, or raffinose) and different lengths and numbers of alkyl chains [formed from lauric (C₁₂) or palmitic (C₁₆) acid]. Analogous anionic sugar ester surfactants, formed by attaching an α-sulfonyl group adjacent to the ester bond, and sugar esters with α-alkyl substituents were also studied. It was found that variations in sugar head group size or in alkyl chain length and number do not significantly affect biodegradability. In contrast, the biodegradation rate of sugar esters with α-sulfonyl or α-alkyl groups, although sufficient for them to be classified as readily biodegradable, was dramatically reduced compared to that of the unsubstituted sugar esters. An understanding of the relationship between structure and biodegradability provided by the results of this study will aid the targeted design of readily biodegradable sugar ester surfactants for use in consumer products.