Improving the Efficiency of Dehydrogenation Catalyst Resource while Reducing the H2 Gas Circulation Rate

In the research the various ways of increasing the selectivity of the dehydrogenation process and reducing the intensity of coke formation have been studied. All results were received by means of the mathematical model of the dehydrogenation process with the calculating technique of optimal water flow. The main conclusion consists in the fact that the decrease in molar ratio H2/feed leads to increasing the catalyst deactivation by coke. It can be partially compensated by increasing the supplied water flow to the reactor to 13-14 l/h instead of 9-10 l/h at the end of cycle. Reducing the life of the catalyst to 270-290 days even at an increased water flow is determined by the intensity of the coking reactions. However, the economic feasibility of operating in such condition causes a considerable increase in production of LAB to 181-186 t/day.     

Turbulence modelling and role of compressibility on oil spilling from a damaged double hull tank

The viscosity plays an important role, and a multiphase solver is necessary to numerically simulate the oil spilling from a damaged double hull tank (DHT). However, it is uncertain whether turbulence modelling is necessary, which turbulence model is suitable; and what the role of compressibility of the fluids is. This paper presents experimental and numerical investigations to address these issues for various cases representing different scenarios of the oil spilling, including grounding and collision. In the numerical investigations, various approaches to model the turbulence, including the large eddy simulation (LES), direct numerical simulation and the Reynolds average Navier–Stokes equation (RANS) with different turbulence models, are employed. Based on the investigations, it is suggested that the effective Reynolds numbers corresponding to both oil outflow and water inflow shall be considered when classifying the significance of the turbulence and selecting the appropriate turbulence models. This is confirmed by new lab tests considering the axial offset between the internal and the external holes on two hulls of the DHT. The investigations conclude for numerically simulating oil spilling from a damaged DHT that when the effective Re is smaller the RANS approaches should not be used and LES modelling should be employed; while when the effective Reynolds numbers is large, the RANS models may be used as they can give similar results to LES in terms of the height of the mixture in the ballast tank and discharge but costing much less CPU time. The investigation on the role of the compressibility of the fluid reveals that the compressibility of the fluid may be considerable in a small temporal‐spatial scale but plays an insignificant role on macroscopic process of the oil spilling. Copyright © 2016 John Wiley & Sons, Ltd.     

A Water Molecule Triggers Guest Exchange at a Mono-Zinc Centre Confined in a Biomimetic Calixarene Pocket: a Model for Understanding Ligand Stability in Zn Proteins

In this study, the ligand exchange mechanism at a biomimetic Zn^II centre, embedded in a pocket mimicking the possible constrains induced by a proteic structure, is explored. The residence time of different guest ligands (dimethylformamide, acetonitrile and ethanol) inside the cavity of a calix[6]arene-based tris(imidazole) tetrahedral zinc complex was probed using 1D EXchange SpectroscopY NMR experiments. A strong dependence of residence time on water content was observed with no exchange occurring under anhydrous conditions, even in the presence of a large excess of guest ligand. These results advocate for an associative exchange mechanism involving the transient exo-coordination of a water molecule, giving rise to 5-coordinate Zn^II intermediates, and inversion of the pyramid at the Zn^II centre. Theoretical modelling by DFT confirmed that the associative mechanism is at stake. These results are particularly relevant in the context of the understanding of kinetic stability/lability in Zn proteins and highlight the key role that a single water molecule can play in catalysing ligand exchange and controlling the lability of Zn^II in proteins.     

Statistical inference and modelling of momentum in stock prices

The following results are obtained, (i) It is possible to obtain a time series of market data {y(t)} in which the fluctuations in fundamental value have been compensated for. An objective test of the efficient market hypothesis (EMH), which would predict random correlations about a constant value, is thereby possible, (ii) A time series procedure can be used to determine the extent to which the differences in the data and the moving averages are significant. This provides a model of the form y(t)-y(t-l)=0.5{y(t- l)-y(t-2)}+ε(t)+0.8ε(r-1) where ε(t) is the error at time t, and the coefficients 0.5 and 0.8 are determined from the data. One concludes that today's price is not a random perturbation from yesterday's; rather, yesterday's rate of change is a significant predictor of today's rate of change. This confirms the concept of momentum that is crucial to market participants. (iii) The model provides out-of-sample predictions that can be tested statistically. (iv) The model and coefficients obtained in this way can be used to make predictions on laboratory experiments to establish an objective and quantitative link between the experiments and the market data. These methods circumvent the central difficulty in testing market data, namely, that changes in fundamentals obscure intrinsic trends and autocorrelations. This procedure is implemented by considering the ratio of two similar funds (Germany and Future Germany) with the same manager and performing a set of statistical tests that have excluded fluctuations in fundamental factors. For the entire data of the first 1149 days beginning with the introduction of the latter fund, a standard runs test indicates that the data is 29 standard deviations away from that which would be expected under a hypothesis of random fluctuations about the fundamental value. This and other tests provide strong evidence against the efficient market hypothesis and in favour of autocorrelations in the data. An ARIMA time series finds strong evidence (9.6 and 21.6 standard deviations in the two coefficients) that the data is described by a model that involves the first difference, indicating that momentum is the significant factor. The first quarter's data is used to make out-of-sample predictions for the second quarter with results that are significant to 3 standard deviations. Finally, the ARIMA model and coefficients are used to make predictions on laboratory experiments of Porter and Smith in which the intrinsic value is clear. The model's forecasts are decidedly more accurate than that of the null hypothesis of random fluctuations about the fundamental value.     

EFFECTIVE SPECIFIC HEATS OF MULTI-PHASE THERMOELASTIC COMPOSITES

This paper studies the effective properties of multi-phase thermoelastic composites. Based on the Helmholtz free energy and the Gibbs free energy of individual phases, the effective elastic tensor, thermal-expansion tensor, and specific heats of the multi-phase composites are derived by means of the volume average of free-energies of these phases. Particular emphasis is placed on the derivation of new analytical expressions of effective specific heats at constant-strain and constant-stress situations, in which a modified Eshelby’s micromechanics theory is developed and the interaction between inclusions is considered. As an illustrative example, the analytical expression of the effective specific heat for a three-phase thermoelastic composite is presented.     

Closed paths of light trapped in a closed Fermat curve

Geometric constructions have previously been shown that can be interpreted as rays of light trapped either in polygons or in conics, by successive reflections. The same question, trapping light in closed Fermat curves, is addressed here. Numerical methods are used to study the behaviour of the reflection points of a triangle when the degree of the curve varies, including a generalization to non integer powers.     

Supplier quality improvement: The value of information under uncertainty

We consider supplier development decisions for prime manufacturers with extensive supply bases producing complex, highly engineered products. We propose a novel modelling approach to support supply chain managers decide the optimal level of investment to improve quality performance under uncertainty. We develop a Poisson–Gamma model within a Bayesian framework, representing both the epistemic and aleatory uncertainties in non-conformance rates. Estimates are obtained to value a supplier quality improvement activity and assess if it is worth gaining more information to reduce epistemic uncertainty. The theoretical properties of our model provide new insights about the relationship between the degree of epistemic uncertainty, the effectiveness of development programmes, and the levels of investment. We find that the optimal level of investment does not have a monotonic relationship with the rate of effectiveness. If investment is deferred until epistemic uncertainty is removed then the expected optimal investment monotonically decreases as prior variance increases but only if the prior mean is above a critical threshold. We develop methods to facilitate practical application of the model to industrial decisions by a) enabling use of the model with typical data available to major companies and b) developing computationally efficient approximations that can be implemented easily. Application to a real industry context illustrates the use of the model to support practical planning decisions to learn more about supplier quality and to invest in improving supplier capability.     

Compressive advection and multi‐component methods for interface‐capturing

This paper develops methods for interface‐capturing in multiphase flows. The main novelties of these methods are as follows: (a) multi‐component modelling that embeds interface structures into the continuity equation; (b) a new family of triangle/tetrahedron finite elements, in particular, the P₁DG‐P₂(linear discontinuous between elements velocity and quadratic continuous pressure); (c) an interface‐capturing scheme based on compressive control volume advection methods and high‐order finite element interpolation methods; (d) a time stepping method that allows use of relatively large time step sizes; and (e) application of anisotropic mesh adaptivity to focus the numerical resolution around the interfaces and other areas of important dynamics. This modelling approach is applied to a series of pure advection problems with interfaces as well as to the simulation of the standard computational fluid dynamics benchmark test cases of a collapsing water column under gravitational forces (in two and three dimensions) and sloshing water in a tank. Two more test cases are undertaken in order to demonstrate the many‐material and compressibility modelling capabilities of the approach. Numerical simulations are performed on coarse unstructured meshes to demonstrate the potential of the methods described here to capture complex dynamics in multiphase flows. Copyright © 2015 John Wiley & Sons, Ltd.     

Modelling of high-temperature dark current in multi-quantum well structures from MWIR to VLWIR

In this paper, a model to calculate the dark current of quantum well infrared photodetectors at high-temperature regime is presented. The model is derived from a positive-definite quantum probability-flux and considers thermionic emission and thermally-assisted tunnelling as mechanisms of dark current generation. Its main input data are the wave functions obtained by time-independent Schrodinger equation and it does not require empirical parameters related to the transport of carriers. By means of this model, the dark current of quantum well infrared photodetectors at high-temperature regime is investigated with respect to the temperature, the barrier width, the applied electric field and the position of the first excited state. The theoretical results are compared with experimental data obtained from lattice-matched InAlAs/InGaAs, InGaAsP/InP on InP substrate and AlGaAs/GaAs structures with rectangular wells and symmetric barriers, whose absorption peak wavelengths range from MWIR to VLWIR. The corresponding results are in a good agreement with experimental data at different temperatures and at a wide range of applied electric field.     

Estimation of viscosities of 1-alkyl-3-methylimidazolium ionic liquids over a range of temperatures using a simple correlation

In this study, a new correlation is proposed for estimating 1-alkyl-3-methylimidazolium ionic liquid (IL) viscosities at different temperatures and atmospheric pressure. Since ILs are rather novel, many of their physical properties are still unavailable. Because of this limitation, the aim of this work was to propose a correlation with a new insight and approach, which requires a minimum number of physical properties as input parameters. In addition to minimal dependency on physical properties, further goals in the development of the model were generality, ease-of-use, simplicity and high accuracy. A total of 2073 literature viscosity datapoints at different temperatures for 38 different ILs were used and a correlation was developed which satisfied the above-mentioned goals. The IL viscosity models of Lazzús and Pulgar-Villarroel, and Gardas and Coutinho were compared to the proposed correlation. More reliable results were obtained by the proposed relation in comparison to literature models.