Development of enhanced three-dimensional printed packings for scale-up of distillation columns: A successful case study

This publication presents a general approach for the enhancement of packings regarding scalability, separation efficiency, and fluid dynamic properties using three-dimensional (3D) printing. The methodology is used to develop miniaturized, scalable packings for process development, and scale-up applications. For this purpose, a 3D printable computer-aided design version of the Rombopak 9M industrial packing (RP9M-3D), which is known for its positive scalability properties, was created. An initial characterization by means of computational fluid dynamics simulations and mass transfer measurements reveals positive but also negative design properties. These findings are used to create a more advanced, miniaturized packing structure, the XW-Pak. The evolved structure is compared to the RP9M-3D. The simulation and experimental results show that the enhanced packing, which is still in the early stages of development, exhibits higher separation efficiencies with improved scalability properties at the same void fraction and surface area than the RP9M-3D.     

Chemical analysis of volatiles emitted by Pinus svlvestris after induction by insect oviposition

Gas chromatography – mass spectrometry analyses of the headspace volatiles of Scots pine (Pinus sylvestris) induced by egg deposition of the sawfly Diprion pini were conducted. The odor blend of systemically oviposition-induced pine twigs, attractive for the eulophid egg parasitoid Chrysonotomyia ruforum, was compared to volatiles released by damaged pine twigs (control) that are not attractive for the parasitoid. The mechanical damage inflicted to the control twigs mimicked the damage by a sawfly female prior to egg deposition. The odor blend released by oviposition-induced pine twigs consisted of numerous mono- and sesquiterpenes, which all were also present in the headspace of the artificially damaged control twigs. A quantitative comparison of the volatiles from oviposition-induced twigs and controls revealed that only the amounts of (E)--farnesene were significantly higher in the volatile blend of the oviposition-induced twigs. Volatiles from pine twigs treated with jasmonic acid (JA) also attract the egg parasitoid. No qualitative differences were detected when comparing the composition of the headspace of JA-treated pine twigs with the volatile blend of untreated control twigs. JA-treated pine twigs released significantly higher amounts of (E)--farnesene. However, the JA treatment induced a significant increase of the amount of further terpenoid components. The release of terpenoids by pine after wounding, egg deposition, and JA treatment is discussed with special respect to (E)--farnesene.     

Influence of preheating of fly ash precursors to produce geopolymers

This study has been focused on the effect of pretreatment of FA and POFA after geopolymerization on the mechanical properties. The aim of this work was to simplify the pretreatment that it can easily industrial be applied, using existing technology. Previous work has shown that a reduction in particle size increases the mechanical properties. However, this method involves a milling process which is not applicable for a wide industrial application. Hence, FA and POFA particles have been heated to 300°C, 500°C, and 800°C but applying different pretreatments: (i) predried at 110°C (reference sample); (ii) as received; (iii) prewetted; (iv) prewetted and later quenched in cold water. It was found that during the treatment the particle size increased due to thermal stress cracking. During fast heating, trapped pore water cannot be removed as fast as it evaporates and hence the particles crack. This increase in particle size caused an increase in compressive strength. In addition, heating to 300°C and 500°C caused a dehydroxylation of FA and POFA. This dehydroxylation resulted in a higher initial reactivity, reducing the setting time and improved mechanical strength.     

Metal Organic Frameworks for Natural Gas Storage in Vehicles

With the increasing demand for alternative fuels the storage of natural gas (NG) in adsorbents like metal organic frameworks (MOFs) will become more important. In order to use MOFs as storage media in fuel delivery systems, the optimization of mass and energy transfer of the system is crucial. For rapid NG filling of a tank, molecules need to reach the adsorption sites within a reasonable time while the heat of adsorption should be dissipated to the environment. In this article, mass transfer in shaped bodies of MOFs was determined by permeability measurements and pulsed field gradient (PFG) NMR spectroscopy. The heat dissipation was also experimentally measured and both data sets were used to set up a theoretical density function theory model to predict the behavior of MOFs for NG storage.     

Measurement of Aerosol Organic Compounds Using a Novel Collection/Thermal-Desorption PTR-ITMS Instrument

We report the development and characterization of a proton-transfer-reaction ion trap mass spectrometer for the speciated measurement of organic compounds in atmospheric aerosols and show results from its first field deployment. The instrument uses an aerosol collection inlet to accumulate aerosol mass followed by rapid thermal desorption to volatilize the organic compounds for in situ analysis. We have performed laboratory studies to characterize instrument performance and the instrument was deployed aboard a NOAA research vessel during the Texas Air Quality Study 2006/Gulf of Mexico Atmospheric Composition and Climate Study (TexAQS 2006/GoMACCS) in August–September 2006. The laboratory-determined detection limit for glutaric acid in mixed glutaric acid/NH ₄ HSO ₄ test aerosols was 0.22 ng collected mass, which corresponds to an estimated detection limit of 12 ng m^?3 for a 10 min sample based on the instrument sample flow rate of 1.8 L min^?1. During TexAQS 2006/GoMACCS, signals well above the detection limit were observed at a number of mass to charge ratios, mostly occurring during an extended period of active pollution photochemistry, but also including detection of possible primary emissions of aerosol-phase pyridine.     

Disorder effects on the strain response of model polymer networks

Molecular dynamics simulations are used to investigate polymer networks made by either end-linking or randomly crosslinking a melt of linear precursor chains. The resulting network structures are very different, since end-linking leads to nearly ideal monodisperse networks, while random crosslinking leads to polydisperse networks, characterized by an exponential strand length distribution. Networks with average strand length 20 and 100 were generated. These networks were used to study the effects of disorder in the network connectivity on observables averaged either over the entire network or selected sub-structures. Heterogeneities in the randomly crosslinked networks cause significant differences in the localization of monomers, however, neither the localization of crosslinks nor the microscopic strain response are significantly affected. Compared to end-linked networks, randomly crosslinked networks have a slightly increased tube diameter, and as a result a slightly decreased shear modulus, but otherwise identical stress-strain behavior. For the investigated systems, we conclude that the microscopic strain response, tube diameter, and stress-strain relation are all insensitive to the heterogeneities due to the linking process by which the network were made.     

Synthesis of 6,6- and 7,7-Difluoro-1-acetamidopyrrolizidines and Their Oxidation Catalyzed by the Nonheme Fe Oxygenase LolO

LolO, a 2-oxoglutarate-dependent nonheme Fe oxygenase, catalyzes both the hydroxylation of 1-exo-acetamidopyrrolizidine (AcAP), a pathway intermediate in the biosynthesis of the loline alkaloids, and the cycloetherification of the resulting alcohol. We have prepared fluorinated AcAP analogues to aid in continued mechanistic investigation of the remarkable LolO-catalyzed cycloetherification step. LolO was able to hydroxylate 6,6-difluoro-AcAP (prepared from N,O-protected 4-oxoproline) and then cycloetherify the resulting alcohol, forming a difluorinated analogue of N-acetylnorloline and providing evidence for a cycloetherification mechanism involving a C(7) radical as opposed to a C(7) carbocation. By contrast, LolO was able to hydroxylate 7,7-difluoro-AcAP (prepared from 3-oxoproline) but failed to cycloetherify it, forming (1R,2R,8S)-7,7-difluoro-2-hydroxy-AcAP as the sole product. The divergent LolO-catalyzed reactions of the difluorinated AcAP analogues provide insight into the LolO cycloetherification mechanism and indicate that the 7,7-difluorinated compound, in particular, may be a useful tool to accumulate and characterize the iron intermediate that initiates the cycloetherification reaction.     

TEMPO‐controlled radical suspension polymerization of poly(styrene)‐block‐poly(styrene‐co‐acrylonitrile) and poly(styrene)‐block‐poly(styrene‐co‐butyl methacrylate)

Suspension polymerization expands the study of controlled radical polymerization to high conversions and is known as a method to synthesize polymers with high molecular weights. The radical block copolymerizations of styrene (S) and acrylonitrile (AN) or butyl methacrylate (BUMA) controlled by 2,2,6,6‐tetramethylpiperidine‐N‐oxyl (TEMPO) was performed in an oil/water pressure reactor system at a temperature of 125°C. TEMPO‐terminated styrene homopolymer was employed as macroinitiator. The systems were examined by varying the composition of the monomer mixture at a constant reaction time, as well as by varying the reaction time for a characteristic monomer composition to get all of the possible conversion range. The solubility effects of acrylonitrile in the suspension medium were considered. Furthermore, the yield of the reaction was improved through initiator addition by taking control of the reaction. The polymerizations could proceed under control up to a conversion of 80–90%. By using the copolymerization equations, the solubility of pure acrylonitrile in the suspension medium could be calculated and was found to be 8 wt.‐%.     

LanV, a bifunctional enzyme: aromatase and ketoreductase during landomycin A biosynthesis

LanV is involved in the biosynthesis of landomycin A. The exact function of this enzyme was elucidated with combinatorial biosynthesis by using Streptomyces fradiae mutants that produce urdamycin A. After expression of lanV in S. fradiae DeltaurdM, which is a mutant that accumulates rabelomycin, urdamycinon B and urdamycin B were found to be produced by the strain. This result indicates that LanV is involved in the 6-ketoreduction of the angucycline core, which preceeds a 5,6-dehydration reaction. 9-C-D-Olivosyltetrangulol was also produced by this strain; this demonstrates that LanV catalyses the aromatization of ring A of the angucycline structure. Coexpression of lanV and lanGT2 in S. fradiae AO, a mutant that lacks all four urdamycin glycosyltransferases, resulted in the production of tetrangulol and the glycoside landomycin H, both of which have an aromatic ring A. As glycosylated angucyclines were not observed after expression of lanGT2 in the absence of lanV, we conclude that LanGT2 needs an aromatized ring A for substrate recognition.     

Dressing and truing of hybrid bonded CBN grinding tools using a short-pulsed fibre laser

This paper presents the results of an investigation into the dressing and truing of hybrid bonded (metal-vitrified) CBN grinding wheels using a short-pulsed fibre laser. Truing of complex contours on CBN grinding tools with sharp edges (edge radii of less than 20 μm) could be successfully applied, whereas other dressing methods have been neither technically nor economically successful. Sharpening by laser can provide the same wheel surface topography which is conventionally produced by SiC and/or Al₂O₃ sharpening tools. Grinding characteristics and long-term performance of the laser-profiled tools are discussed.