Incorporating experimental uncertainties into multivariate granulation modelling

A methodology that carries experimental uncertainties into model predictions is studied and applied to a multidimensional population balance model for granulation processes. This complex model contains 27 parameters. A portion of them such as material constants can be measured or estimated, whereas some of the model parameters need to be established through granulation experiments and subsequent fitting to the model. As uncertainties are associated with every measurement, these are used in the presented methodology for the computation of uncertainties in the model predictions. This allows one to assess the quality of a model and to identify outliers in the experimental observations. As the evaluation of the complex model framework is computationally expensive, the granulation process is approximated with response surfaces in the studied example, allowing the quick computation of the model response in the optimisation procedure. Using eight sets of experimental observations, model-specific rate constants for particle coalescence, compaction, breakage, and reaction are calculated. Additionally, uncertainties of these parameters are estimated, allowing for the calculation of the model prediction and its uncertainty. Whereas the a priori uncertainties are relatively large, the uncertainties are significantly reduced by the method proposed. In addition to this, a possible mismatch between the model and the experimental observations is identified, giving hints for further investigations.     

Efficient Trifluoromethylation of Activated and Non‐Activated Alkenyl Halides by Using (Trifluoromethyl)trimethylsilane

An efficient method for the trifluoromethylation of halogenated double bonds by using in situ generated “trifluoromethyl copper” is described. Herein, the most common trifluoromethyl source, (trifluoromethyl)trimethylsilane, was converted selectively into “trifluoromethyl copper” by using copper iodide as copper source and potassium fluoride as promoter. In 1,3‐dimethyl‐3,4,5,6‐tetrahydro‐2(1H)‐pyrimidinone (DMPU) as chelating solvent the trifluoromethylation of activated and non‐activated alkenyl halides occurred mostly in good to excellent yields in up to a gram scale.     

Dynamical Screening and Electron-Mediated Superconductivity in Intercalated Layered Metallochloronitrides

Metallochloronitrides are layered conductors that have recently been found to superconduct at critical temperatures up to T _c 26 K. It is known that the electron–phonon interaction is small in these systems, so that the conventional pairing mechanism through exchange of phonons is unable to provide for such high T _cs. We show that the dominant contribution to the pairing interaction in these materials comes from the exchange of low-energy collective modes, specific to layered conductors. The existence of such acoustic plasmons results from the incomplete screening of the Coulomb interaction perpendicular to the conducting planes which expresses itself in the dynamical nature of the screened Coulomb interaction.     

Determination of fatty acid derivatives in fuel and diesel oil

Fuel oil plays one of the most important roles as thermal energy source in domestic application. Due to its common use, a careful monitoring of the grade and the deviation of the quality is required. Recently it has been observed that the presence of polar fatty acid derivatives is leading to problems in the fuel injection systems and consequently can cause a damage of the engine. A fast and reliably working procedure is presented, which allows the group determination of these polar compounds, namely glycerides, soaps and fatty acids. A sample preparation succeeded, which accomplishes the extraction, the clean up and the derivatization in one single reaction vessel. Derivatives were methylated with acetyl chloride and methanol and quantified with gas chromatography mass spectrometry. The complexity of fuel oil requires a careful elaboration of the clean up and the extraction procedure. Owing to the novelty of this procedure an accurate investigation and optimization of influential parameters were performed. Optimum conditions for the solid phase extraction with polar sorbents were provided for all target compounds. Additionally, the necessity of the clean up is shown with the relation between investigated analytes and matrix effects. Finally, method performance was verified with an accurate validation and analyses of spiked samples.     

Influence of mass transfer on thermogravimetric analysis of combustion and gasification reactivity of coke

Non-isothermal TG/DTG measurements are widely used to determine kinetic parameters of oxidation and gasification of carbons, e.g. by multi-heating rate methods. Thereby it is important to avoid spurious effects due to diffusion limitations. In this work, TG/DTG experiments with activated carbon were conducted under isothermal and non-isothermal conditions. The agreement of the experimental results with results of simulations based on the intrinsic kinetics, pore diffusion and external diffusion in/to the sample (crucible) is very good. The simulations show that mass transfer has an unwanted influence on TG measurements, if the concentration of the gaseous reactant (O₂ and CO₂) is too low and/or the heating rate is too high. Based on literature data, the simulation was extended to blast furnace coke with a very low reactivity and to highly reactive coke from pyrolysis of miscanthussinensis. The simulations and theoretical considerations lead to a criterion to exclude the influence of mass transfer on TG measurements a priori. This criterion is valid for combustion as well as for gasification with steam or carbon dioxide.     

High resolution experimental measurement of turbulent flow field in a high pressure homogenizer model and its implications on turbulent drop fragmentation

Particle image velocimetry is performed on a model of a high pressure homogenizer, scaled for qualitative similarity of the one phase turbulent flow field in a production scale homogenizer. Flow fields in gap entrance, gap and gap outlet chamber are obtained with high resolution. The measurements show gap flow development and formation of a turbulent wall adherent jet when exiting into the outlet chamber. Turbulent kinetic energy spectra show how the turbulent energy available for fragmentation is transported over distance along the jet centre axis.The high resolution images are also used together with a Kolmogorov–Hinze theory framework for discussing drop fragmentation together with a direct evaluation of disruptive stresses from measurements. For the turbulent inertial mechanism large drops experience high fragmenting force close to eight gap heights downstream of the gap exit whereas this occurs closer to 20 gap heights for smaller drops. The turbulent viscous mechanism is most efficient at a downstream distance of eight gap heights into the outlet chamber for all drops sizes.