Studies on the Autoxidation of Phenylacetylene

Phenylacetylene is oxidized slowly by molecular oxygen at 110°C. The main oxidation products are benzoic acid, benzoic anhydride, and benzaldehyde. Besides the oxidation, thermal dimerization, oligomerization, and polymerization processes also take place. As individual products 1,4-diphenylbut-1-yn-3-ene and 1,3,5-triphenylbenzene were identified. About 80% of the phenylacetylene consumed are converted into products of low volatility which could not be detected by gas chromatography. The autoxidation of acetylenic hydrocarbones [1] preferably yields products of the attack at C H bonds in α-position to the CC triple bond. An attack at the CC riple bond was a first proved in the case of phenylacetylene, which besides polymeric products yielded benzaldehyde, acetophenone, and organic acids [2]. Later, in the causes of the isomeric octynes [3] and of various 1-Phenylalk-1-ynes [4] an attack at the CC triple bond was also proved. As the primary products of the oxidative attack at the CC triple bond short-lived oxirenes or their valence isomers, the corresponding ketocarbenes are to be expected. Indeed, their rearrangement products were found in the oxidation mixtures of both the isomeric ocytnes [3] and the 1-phenylalk-1-ynes [4]. Other products of the oxidative attack at the CC triple bond are lower carboxylic acids, formally produced by oxidative cleavage of the CC triple bond [3, 4].     

Imazalil Degradation upon Applying Ozone—Transformation Products,Kinetics, and Toxicity of Treated Aqueous Solutions

The elimination of the pesticide imazalil (IMZ) spiked into ultrapure water as well as into wastewater applying ozone (O₃) and the identification of transformation products was investigated. O₃ under hydroxyl radical suppression conditions reacted rapidly with the aliphatic double bond or the imidazole ring in IMZ, yielding several transformation products by partial oxidation. The structures of four oxidation products not yet described were characterized and identified after liquid chromatography coupled with high resolution, high mass accuracy, mass and tandem mass spectrometry (LC/MS and -MSⁿ) in ultrapure water. For two identified transformation products, generated via direct ozone attack on IMZ, formation pathways were proposed. In wastewater, only two of those transformation products were observed. Kinetics studies for the reaction of IMZ with O₃, evaluated by the competition kinetic method, resulted in a second-order rate constant k_O3,IMZ ～ (1.02 ± 0.03)?×?10⁵ M^?1 s^?1 at pH 6.6 ± 0.2, indicating that IMZ is completely transformed during the ozonation process. Tests of acute toxicity were performed applying a solution of IMZ in ultrapure water or treated wastewater to Daphnia magna. In both cases the decrease of toxicity was observed after ozone treatment.     

Ozone Treatment of Tannery Wastewater Monitored by Conventional and Substance Specific Wastewater Analyses

Ozone is an unstable and highly reactive gas applied in drinking water or wastewater treatment to oxidize and/or mineralize pollutants. Its application in wastewater treatment leads to a destruction of persistent pollutants combined with an improvement of biodegradability. The oxidation of organic and inorganic compounds in tannery wastewater at different pHs applying O₃ was studied. Results after O₃-treatment were determined by conventional wastewater parameters, e.g., total organic carbon (TOC), biochemical oxygen demand after 5 days (BOD₅), and chemical oxygen demand (COD), as well as by substance-specific mass spectrometric analytical techniques, i.e., gas chromatography—mass spectrometry (GC/MS) and liquid chromatography—mass and tandem mass spectrometry (LC/MS and—MSⁿ). In parallel, variations in the toxicity of the tannery wastewater against water organisms before and after O₃-treatment were determined by means of biotoxicity testing, i.e., Daphnia magna Straus and Vibrio fischeri bioassays.     

Development of a qualitative test method for the cleanability of polymer woven filter media

In this paper a new method for cleaning of filter media is presented, and the cleanability with different textures and surface finishes is compared. With the method described, it is possible to evaluate the quality of the cleaning process. According to the German VDMA standard cleaning test, riboflavin and malt extract are applied as model contaminants for evaluation of the cleaning results. To compare the cleanability of filter media with different properties and geometries the results are adapted to the law of mass transfer and to the Sherwood number, a dimensionless parameter describing the quality of a cleaning process.     

Evaluation of pathways for washing soluble solids

Filter cake washing is a purification method for particulate products in liquids. This process is mostly one step of a sequence in a solid–liquid separation process. For soluble products not only the mechanical transport mechanisms in washing but also the dissolution process of the product must be considered in order to describe the washing process appropriately. An unconsidered dissolution may cause problems and often severe product loss depending on the material properties. This paper presents several methods of soluble solids washing including filter cake washing by pressure and centrifugal forces as well as moving bed washing. The advantages and drawbacks of each method are discussed to evaluate the suitability of its technical application.     

Characterization of Pt/SBA-15 prepared by the deposition–precipitation method

Mesoporous silica SBA-15 was prepared and loaded with Pt using the deposition–precipitation method (DP). The Pt loaded material was characterized by N₂ sorption, and X-ray diffraction (XRD) at low scattering angles as well as XRD at wide angles, in order to monitor the impact of the metal deposition pathway on the mesoporous texture. After DP the material contains ordered mesoporous silica as well as a fraction appearing as non-ordered amorphous silica. This is most likely caused by the hydrothermal treatment involved in the DP. The material was also characterized using NIR and ²⁹Si MAS NMR spectroscopy. The NIR results of the calcined materials indicate that the silanol groups of SBA-15 may act as anchoring groups for the metallic Pt particles. The NMR spectroscopy data shows that the Pt/SBA-15 sample prepared by the DP method posseses a better short-range regularity of SBA-15 walls as compared to the parent SBA-15. This is suggested to be caused by dissolution and possible re-precipitation of siliceous species.     

ZSM-5 zeolite films on Si substrates grown by in situ seeding and secondary crystal growth and application in an electrochemical hydrocarbon gas sensor

ZSM-5 zeolite films were grown on Si substrates by a two-step hydrothermal synthesis consisting of in situ seeding and secondary crystal growth. The films were 8–13 μm thick and partly oriented with the c-axis perpendicular to the substrate surface. After ion exchange with sodium ions, one film was applied as solid electrolyte in a potentiometric hydrocarbon gas sensor. A fast and reversible voltage response of the sensor to varying propane concentrations (100 ppm – 10%) was observed in O₂/CO₂/N₂ gas mixtures at 723 K.     

The Chemistry of the Postpharyngeal Gland of Female European Beewolves

Females of the European beewolf, Philanthus triangulum, possess a large glove-shaped gland in the head, the postpharyngeal gland (PPG). They apply the content of the PPG to their prey, paralyzed honeybees, where it delays fungal infestation. Here, we describe the chemical composition of the gland by using combined GC-MS, GC-FTIR, and derivatization. The PPG of beewolves contains mainly long-chain unsaturated hydrocarbons (C23–C33), lower amounts of saturated hydrocarbons (C14–C33), and minor amounts of methyl-branched hydrocarbons (C17–C31). Additionally, the hexane-soluble gland content is comprised of small amounts of an unsaturated C25 alcohol, an unknown sesquiterpene, an octadecenylmethylester, and several long-chain saturated (C25, C27) and unsaturated (C23–C27) ketones, some of which have not yet been reported as natural products. Surprisingly, we found a dimorphism with regard to the major component of the PPG with some females having (Z)-9-pentacosene, whereas others have (Z)-9-heptacosene as their predominant component. The biological relevance of the compounds for the prevention of fungal growth on the prey and the significance of the chemical dimorphism are discussed.     

H2 rich syngas by selective CO2 removal from biomass gasification in a dual fluidized bed system — Process modelling approach

A process model of dual fluidized bed gasification is presented based on mass- and energy balances. The model further covers the evaluation of thermodynamic equilibrium states. The gasification is investigated for the special case that CaO/CaCO₃ is used as bed material allowing selective transport of CO₂ from the gasification reactor to the combustion reactor by repeated carbonation and calcination. Experimental data are used to determine the model parameters. An empirical approach towards the kinetics of fuel conversion allows prediction of process behaviour at varied fuel water content. The selective transport of CO₂ results in high H₂ contents in the produced syngas. The lower operating temperatures in the gasification reactor increase the efficiency of energy conversion. The results are in agreement with experimental data and show the thermodynamic limitations of the technology.