A compact photomicroreactor design for kinetic studies of gas‐liquid photocatalytic transformations

A compact photomicroreactor assembly consisting of a capillary microreactor and small‐scale light emitting diodes was developed for the study of reaction kinetics in the gas‐liquid photocatalytic oxidation of thiophenol to phenyl disulfide within Taylor flow. The importance of photons was convincingly shown by a suction phenomenon due to the fast consumption of oxygen. Mass transfer limitations were evaluated and an operational zone without mass transfer effects was chosen to study reaction kinetics. Effects of photocatalyst loading and light sources on the reaction performance were investigated. Reaction kinetic analysis was performed to obtain reaction orders with respect to both thiophenol and oxygen based on heterogeneous and homogeneous experimental results, respectively. The Hatta number further indicated elimination of mass transfer limitations. Reaction rate constants at different photocatalyst loadings and different photon flux were calculated. Furthermore, the advantages of this photomicroreactor assembly for studying gas‐liquid photocatalytic reaction kinetics were demonstrated as compared with batch reactors. © 2015 American Institute of Chemical Engineers AIChE J, 61: 2215–2227, 2015     

Production of Particle‐Stabilized Nonspherical Emulsion Drops in Simple Shear Flow

Nonspherical drops are of interest in the formation of microcapsules in life sciences like food, pharmacy, and cosmetics, agro and fine chemicals as well as material sciences. Out of many systems, particle‐stabilized emulsion drops, so‐called Pickering emulsions, exhibit an interesting formulation. Systems with Pickering particles applied in an excess amount were investigated. During deformation, the particles fully covered the enlarged drop interfaces and prevented its relaxation to a spherical drop shape. Nonspherical drops could be produced in simple shear flow using an adequate process routine. The production in a simple device is a promising high‐throughput alternative to microfluidic devices.     

Characterization of Biomimetic Cofactors According to Stability,Redox Potentials,and Enzymatic Conversion by NADH Oxidase from Lactobacillus pentosus

Oxidoreductases are attractive biocatalysts that convert achiral substrates into products of higher value, but they are also for the most part dependent on nicotinamide cofactors. Recently, biomimetic nicotinamide derivatives have received attention as less costly alternatives to natural cofactors. However, recycling of biomimetics is still challenging because there are only limited opportunities. Here, we have characterized various biomimetic cofactors with regard to stability and redox potentials to find the best alternative to natural cofactors. Further, the cofactor spectrum of NADH oxidase from Lactobacillus pentosus (LpNox) could be expanded, and the enzymatic activity was also compared to activities with different small‐molecule catalysts. As a result, we succeeded in identifying several strategies for regeneration of oxidized biomimetics.     

Kinetic study of hydrogen peroxide decomposition at high temperatures and concentrations in two capillary microreactors

On the background of the direct adipic acid synthesis from cyclohexene and H₂O₂, a kinetic model was derived for the H₂O₂ decomposition catalyzed by sodium tungstate at high H₂O₂ concentrations and high temperatures. A perfluoroalkoxy (PFA) and a stainless steel micro‐flow capillary match commonly used microreactor materials. In the PFA capillary, the decomposition of hydrogen peroxide increased with residence time, reaction temperature and catalyst loading. The reaction order with respect to hydrogen peroxide and sodium tungstate was zero and one, respectively. Simulated data fit well with experimental data in the PFA capillary. While showing a similar trend as that in the PFA capillary, the stainless steel capillary exhibited much higher reaction rates. The steel surface participated in the decomposition process as a heterogeneous catalyst. Key influencing factors of the H₂O₂ decomposition provided some clues on the reaction mechanism of the adipic acid synthesis and its process optimization. © 2016 American Institute of Chemical Engineers AIChE J, 63: 689–697, 2017     

Entwicklung einer kontinuierlichen Mikrowellen‐Vakuumtrocknungsanlage mit hexagonalem Verfahrensraum

A continuous microwave vacuum drying processor with a hexagonal cross‐section of the cavity was constructed. Due to the geometry of the cavity and the continuous movement of the product, homogeneous microwave power absorption of the product can be favored. By the expansion and simultaneous dehydration of non‐expanded, starch‐based extrudates, the applicability of the constructed processor could be shown.     

Modification of Polycarbonate and Glycol Modified Poly(ethylene terephthalate) by Addition of Silica‐Nanoparticles Grafted with SAN Copolymer Using “Classical” and ARGET ATRP

This study presents a nanocomposite manufacturing route starting from non‐functionalized nanosilica and SAN surface modification via “grafting from” ATRP up to processing of transparent polycarbonate and glycol modified poly(ethylene terephthalate) nanocomposites. Synthesis limitations of low molecular weight graft SAN derived from “classical” ATRP are overcome by employment of the emerging ARGET ATRP. Mechanical investigations of polycarbonate and glycol modified poly(ethylene terephthalate) nanocomposites present up to 80% enhancement of creep performance and additionally 70% enhancement against wear abrasion for glycol modified poly(ethylene terephthalate) nanocomposites. Strength and tensile modulus are only moderately influenced by the addition of nanoparticles. Morphological studies confirm that the present modification route is able to create uniform dispersions of single particles and small particle aggregates in polymer matrices.

     

Binding of cadmium,copper, and zinc to humic substances originating from municipal solid waste compost

The application of municipal solid waste (MSW) compost increases both the trace metal loading and the organic matter in the soil. To characterize the quality and metal-binding capacity of the compost OM, we extracted humic acid (HA) and fulvic acid (FA) from mature MSW compost and analyzed them for elemental composition, acid-titratable functional groups, total metal content, and structural components (by ¹³C NMR). HA constituted 67% of all extracted humic substances and differed significantly from HAs of cultivated lands: The compost HA exhibited smaller molecular size, a higher N content, and lower aromaticity due to large amounts of saturated aliphatic components. Metal complexation studies of the extracted HA and FA were performed by equilibrium dialysis titration. The complexing capacity (CC) was highest for Cu: CC_HA = 3357 and CC_FA = 5221 μmol Cu g⁻¹ of dissolved organic carbon (DOC) at pH 5. Zn and Cd were bound (at pH 7) in smaller concentrations: CC_HA(Zn) = 2167, CC_FA(Zn) = 2809, CC_HA(Cd) = 2386, and CC_FA(Cd) = 2468 μmol metal g⁻¹ of DOC. Stability constants for binding on the strongest sites (pK_int) were determined as pK_intHA = 6.6 and pK_intFA = 7.3 for Cu at pH 5; and pK_intHA = 8.0 and pK_intFA = 6.4 for Cd at pH 7. Since these measured parameters fall within the ranges of values obtained for soil humic substances, we conclude that in soils with little organic matter, compost addition will significantly increase the amount of highly reactive organic complexing agents for trace metals in the soil.     

Burn Rate Models for Gun Propellants

In the past, Vieille's law and minor modifications of it described sufficiently the linear burning rate of gun propellants which governs the design of charges by interior ballistic simulations. Recent developments to increase the performance led to new gun concepts and innovative propellants. These are the electrothermal‐chemical gun, porous and foamed charges as well as formulations exhibiting a temperature independent burning. Vieille's law cannot fully meet experimental results in these cases. Approaches based on the heat flow equation in the solid energetic material give simplified formulas to extend the validity. These burning rate models have the ability to describe the experimentally determined burning behavior at least in a simplified or qualitative way. More sophisticated methods consider complex geometrical structures in the solid or take into account the actual progress in phase behavior and reaction kinetics of heterogeneous combustion. The dependence of the burning rate on initial temperature, on phase transitions, porous structure and gaseous reactions can be described.     

连续相黏度对膜乳化结果的影响

Oil-in-water(o/w) emulsions were produced with a membrane emulsification system. The effect of the continuous phase viscosity on the emulsification was studied. The theoretical analyses show that the continuous phase viscosity influences not only the flow field of the continuous phase but also the interfacial tension. The droplet size distribution and disperse phase flux for different continuous phase viscosity were investigated experimentally at constant wall shear stress and constant volume flow rate of the continuous phase respectively.