Inferring kinetic dissolution of NaCl in aqueous glycol solution using a low-cost apparatus and population balance model

An experimental methodology for inferring brine dissolution rate in monoethylene glycol (MEG) solutions at different temperatures using a webcam combined with a mathematical model is presented. The measurement system is designed to track the RGB (red, green, and blue) colour variations during the dissolution process. A dynamic model augmented with the population balance equation is applied to describe the dissolution process. Moreover, the dissolution rate is consistently related to the temperature and MEG concentration through the driving force based on the Gibbs energy and chemical affinity. The applied low-cost measurement apparatus proved to be a useful resource for tracking the dissolution dynamics in a wide range of undersaturation.     

Ionic conductivities and high resolution microscopic evaluation of grain and grain boundaries of cerium-based codoped solid electrolytes

Doped CeGdO and codoped CeGdOSmO compositions were synthesized, giving rise to nanoparticulate powders. Ionic conductivities at bulk and grain boundaries of the sintered samples were determined, exhibiting increased conductivity in the samaria-codoped samples. Scanning electron microscopy (SEM) showed a significant reduction in the grain size of samaria-codoped electrolytes. This reduced grain size of the codoped samples caused a reduction in Schottky barrier height, increasing oxygen vacancy concentration in the space-charge layer of the grain boundary and culminating in greater ionic conductivity in the boundary region. For the gadolinium doped samples, high resolution transmission electron microscopy images at grains showed the presence of large cluster of defects (nanodomains), hindering the movement of charge carriers and reducing ionic conductivity. However, the samaria-codoped system displayed better homogeneity at atomic level, resulting in reduced oxygen vacancy ordering and, consequently, smaller nanodomains and higher bulk (grain) conductivity. The reduced grain sizes and smaller nanodomains caused by codoping favor the ionic conductivity of ceria-based ceramics, doped with gadolinia and codoped with samaria.     

Multivariable control strategy based on bifurcation analysis of an industrial gas-phase polymerization reactor

In an industrial gas-phase polyethylene reactor, the safe operating range of temperature is rather narrow. Even within this temperature range, temperature excursions must be avoided because they can result in low catalyst productivity and significant changes in product properties. If the manipulated variable for temperature control saturates (i.e., the cooling water valve position is completely open), then the reactor operates without a feedback temperature controller, leading to oscillatory behavior and limit cycles. In this work, it has been demonstrated that the saturation in the manipulated variable and the complex non-linear dynamic behavior are removed when auxiliary manipulated variables, obtained by bifurcation analysis, are used in a multivariable control strategy for the reactor temperature control. Two control structures are proposed and compared considering their impact in the reactor production and polymer melt index. In the first control structure, the designed PID controller for the reactor temperature is considered and a switching strategy with a PI controller for the auxiliary manipulated variables is included. In the second control structure, the designed PID controller for the reactor temperature is also used, however, a MPC controller for the auxiliary manipulated variables is considered. The results suggest that the use of gain-scheduling strategy in the PID temperature controller with a MPC controller for the auxiliary manipulated variables avoids the saturation of the manipulated variable and, hence, the undesired non-linear dynamic behavior, reducing the production loss and improving the product quality.     

On the power of deep pushdown stacks

Inspired by recent work of Meduna on deep pushdown automata, we consider the computational power of a class of basic program schemes, NPSDS _s , based around assignments, while-loops and non-deterministic guessing but with access to a deep pushdown stack which, apart from having the usual push and pop instructions, also has deep-push instructions which allow elements to be pushed to stack locations deep within the stack. We syntactically define sub-classes of NPSDS _s by restricting the occurrences of pops, pushes and deep-pushes and capture the complexity classes NP and PSPACE. Furthermore, we show that all problems accepted by program schemes of NPSDS _s are in EXPTIME.     

Platinum supported catalysts for carbon monoxide preferential oxidation: Study of support influence

The aim of this work is to study the influence of the addition of different oxides to an alumina support, on surface acidity and platinum reducibility in platinum-based catalysts, as well as their effect on the activity and selectivity in CO preferential oxidation, in presence of hydrogen. A correlation between surface acidity and acid strength of surface sites and metal reducibility was obtained, being Pt-support interaction a function of the acid sites concentration under a particular temperature range. In platinum supported on alumina catalysts, CO oxidation follows a Langmuir-Hinshelwood mechanism, where O₂ and CO compete in the adsorption on the same type of active sites. It is noteworthy that the addition of La₂O₃ modifies the reaction mechanism. In this case, CO is not only adsorbed on the Pt active sites but also on La₂O₃, forming bridge bonded carbonates which leads to high reactivity at low temperatures. An increase on temperature produces CO desorption from Pt surface sites and favours oxygen adsorption producing CO₂. CO oxidation with surface hydroxyl groups was activated producing simultaneously CO₂ and H₂.     

High-Stable Mesoporous Ni-Ce/Clay Catalysts for Syngas Production

Abstract  

A mesoporous-type catalytic support was synthesized through the modification of a smectite with polyvinyl alcohol (PVA) and microwaves. Texture and micro-morphology of the support was determined. Several techniques were employed in order to describe the chemical environment of active species on the surface. Ni⁰ particle sizes were dependent on the structural site of reducible species. High stable Ni-Ce catalysts (calcined at 800 °C) were evaluated in the CO₂ reforming of methane reaction at 700 °C (WHSV = 96 L g⁻¹ h⁻¹, without dilution gas and pre-reduction). The catalysts have presented CH₄ conversions between 40 and 65%, CO₂ conversion between 35 and 65% and H₂/CO ratios between 0.2 and 0.4.     

Rotating disk electrode analysis of oxygen reduction at platinum particles under limiting diffusion conditions

An analysis is carried out of oxygen reduction under limiting diffusion conditions on a rotating disk electrode partially covered with platinum particles (‘particulate electrode’). First a model is developed for the current response at a rotating particulate electrode, because Levich equation, used for the classical continuous disk electrodes, is not applicable in this case. The model allows for the calculation of the limiting diffusion current by an iterative algorithm, as a function of the density and size of the particles, and the constants for the adsorption/desorption and diffusion of reactants over non-covered areas of the substrate. The model is valid when there is no overlapping of surface diffusion areas around the particles. In a second part, the oxygen reduction on platinum particles electrodeposited on a glassy carbon disk is studied. Platinum particulate electrodes with a variable density and size of particles are prepared by single pulse electrodeposition technique. Limiting diffusion currents for oxygen reduction are analysed on the light of the proposed model. Values for the oxygen surface diffusivity and the equilibrium adsorption/desorption constant on the glassy carbon substrate are obtained from the analysis.     

Efficiency calibration of a HPGe detector in the [46.54–2000] keV energy range for the measurement of environmental samples

Here we describe a general method of calibrating the efficiency of a Ge γ-ray spectrometer. The method, which is based on the work of Quintana and Fernández (Appl. Radiat. Isot. 47 (1996) 911), can now be applied to many different experimental set-ups including both liquid and solid environmental samples. The method requires two different types of experimental inputs. Firstly, it requires measurements with radioactive sources emitting cascades of γ rays covering the energy range of interest. Secondly, it requires measurements with sources emitting isolated γ rays in order to provide coincidence-summing corrections. On this basis, we establish a general function to describe the energy dependence of the efficiency for the particular geometry and source matrix. The method has been applied to 11 different experimental arrangements to provide efficiency calibrations over the range 46.54–2000 keV with associated uncertainties ranging from 0.1% to 1.8%. This allows high precision measurements with environmental samples, which often have very low activities.     

Study of a SOFC with a bimetallic Cu–Co–ceria anode directly fuelled with simulated biogas mixtures

The present work is focused in the study of the bimetallic Cu–Co formulation combined with CeO₂ as SOFC anode, at 750 °C, direct feed of methane and two different fuel mixtures that simulate biogas. Additionally, the sulphur tolerance of new anode material has been evaluated. Its single cell evaluation, based on a samaria doped ceria (SDC) solid electrolyte and a LSM perovskite cathode, together with the electrochemical characterisation and catalytic activity tests, have allowed to demonstrate the ability of this material to operate directly with simulated biogas mixtures without loss of single cell performance due to the formation of carbon deposits or sulphur anode poisoning. The activity of this material for the exothermic oxidation of methane reduces the energy requirement of the endothermic internal methane reforming process. The cobalt doping of basic copper–ceria formulation enhanced sulphur and carbon coking tolerance of the SOFC anode material.