The constrained total least squares technique and its applicationsto harmonic superresolution

The constrained total least squares (CTLS) method is a natural extension of TLS to the case when the noise components of the coefficients are algebraically related. The CTLS technique is developed, and some of its applications to superresolution harmonic analysis are presented. The CTLS problem is reduced to an unconstrained minimization problem over a small set of variables. A perturbation analysis of the CTLS solution is derived, and from it the root mean-square error (RMSE) of the CTLS solution, which is valid for small noise levels, is obtained in closed form. The complex version of the Newton method is derived and applied to determine the CTLS solution. It is also shown that the CTLS problem is equivalent to a constrained parameter maximum-likelihood problem. The CTLS technique is applied to estimate the frequencies of sinusoids in white noise and the angle of arrival of narrowband wavefronts at a linear uniform array. In both cases the CTLS method shows superior or similar accuracy to other advanced techniques     

Kinetics study on cnt‐supported RuKCo FTS catalyst in a fixed bed reactor

The rate of syngas (H₂/CO) consumption over a RuKCo/CNT Fischer–Tropsch synthesis (FTS) catalyst was measured in a fixed bed microreactor at 210–225°C, 2–3.5 MPa, H₂/CO feed molar ratios of 1–2.5, and gas hourly space velocity (GHSV) range of 2700–3600 h^?1. The data have been used to model the kinetics of the FTS reactions within the range of the studied conditions. One empirical power law model and four semi‐empirical kinetic models based on Langmuir–Hinshelwood‐type equation have been evaluated. The best fitting was obtained with the equation: similar to that proposed by Brötz et al. The estimated activation energy (E = 80–85 kJ/mol) is lower than that is reported in the literature. The validity of these results are restricted to fixed beds with the given catalyst in the tested conversion regime.     

In‐line near infrared spectroscopy monitoring of pharmaceutical powder moisture in a fluidised bed dryer: An efficient methodology for chemometric model development

This work proposes a novel chemometric methodology for in‐line near infrared spectroscopy (NIRS) monitoring of pharmaceutical powder moisture in a fluidised‐bed dryer. The collected spectra are analysed by multivariate chemometrics involving the preparation of numerous laboratory samples. A different methodology, using only plant samples, was tested in real‐time. A specially designed probe tip, allowing for robust in‐situ spectral acquisition, was designed. The results prove that NIRS can be as efficient as traditional quality analyses, e.g. loss‐on‐drying, in measuring powder moisture content in a fluidised bed dryer with a calibration model based only on plant samples. © 2011 Canadian Society for Chemical Engineering     

Co‐doped ZnO thin films grown by pulsed electron beam ablation as model nano‐catalysts in fischer‐tropsch synthesis

A single‐step deposition of cobalt‐doped zinc oxide (Co‐ZnO) thin film nano‐composites on three different crystalline substrates, viz., Al₂O₃ (c‐sapphire), silicon (100) (Si), and SiO₂ (quartz) is reported, using pulsed electron beam ablation (PEBA). The results indicate that the type of substrate has no effect on Co‐ZnO films stoichiometry, morphology, microstructure, and film thickness. The findings show the presence of hexagonal close‐packed metallic Co whose content increases in the films deposited on Al₂O₃ and Si substrates relatively to SiO₂ substrate. The potential of the films as model nano‐catalysts has been evaluated in the context of the Fischer‐Tropsch (FT) process. Fuel fractions, which have been observed in FT liquid products, are rich in diesel and waxes. Specifically, Co‐ZnO/Al₂O₃ nano‐catalyst shows a selectivity of ～4%, 31%, and 65% towards gasoline, diesel, and waxes, respectively, while Co‐ZnO/SiO₂ nano‐catalyst shows a selectivity of ～12%, 51%, and 37%, for gasoline, diesel, and waxes, respectively. © 2018 American Institute of Chemical Engineers AIChE J, 64: 3332–3340, 2018     

Dry Reforming of Methane with a Ni/Al2O3‐YSZ Catalyst: The Role of the Catalyst Preparation Protocol

Many studies of Ni based ceramic supporting reforming catalysts are found in the literature. A synthesis of the reported results shows that their efficiency and durability are significantly affected by their fabrication protocol. This research has been aimed at evaluating how the conditions of 1) the ceramic support preparation and 2) the Ni deposition, through an impregnation‐drying‐calcination‐reduction protocol, affect the catalytic activity and the catalyst deactivation over time during methane dry reforming. The catalyst support used in this study was obtained by the mixing and pressing of alumina and YSZ (Yttria Stabilized Zirconia) powders, then calcining the mixtures at high temperature to form pellets of limited porosity (specific surface of 1.5‐10 m²/g), without inducing change to the crystalline phases. The results show that the surface density of the nickel particles, the catalyst activity, and its life span are highly dependent upon the catalyst preparation protocol. The initial nitrate solution concentration, the duration of the impregnation and the specific surface of the ceramic support have, all of them, a considerable influence on the size range of the deposited nickel particles. The surface density, the amount and the size of the latter highly affect the catalytic activity. It has been also shown that an increase in the ratio CH₄/CO₂ is detrimental to the catalytic activity of the tested formulations; a small excess of methane is enough to initiate the deactivation process of the catalyst very quickly for all of the composition tested in this study. A phenomenological deactivation kinetics model has been built and optimized. Although there are differences in deactivation rates among the different formulations tested, the model shows that the deactivation rate is highly dependent upon the reaction rate constant and that zero‐ and first‐order kinetics give statistically the same prediction error; the latter is always lower or equal to the experimental error.     

Potassium chloride caking tendency: A parametric study of cake break energy

Undesired particulate agglomeration can create powder flow issues during manufacturing. Potassium chloride (KCl), a commercial product used in powder form as a potassium source, is known to agglomerate. The main objective is to develop a method to assess KCl agglomeration, then use it to understand its driving forces and the phenomena taking place. Based on industrial data in pharmaceutical manufacturing, the following 5 parameters are considered as critical in terms of agglomeration: conditioning humidity, conditioning time, drying, applied pressure and particle size. Beakers containing 40?g of original or ground KCl powder are compacted under specific humidity conditions in a bell jar. Once the beakers are conditioned, agglomerate hardness tests evaluate agglomeration extent by correlating it with the energy required for powder penetration. This energy is calculated from force-distance curves. The results show that the Area Under the force vs distance Curve (AUC) is a good indicator of agglomeration extent. Thus, the AUC is a scalar and has units of work. Based on AUC analysis, the highest agglomeration is found in conditioning humidity of 85% relative humidity (RH), original particle size, drying and conditioning time of 16?h. The agglomeration of original versus ground particle size powders is further investigated over time in a conditioning test. Preliminary tests validate our method and indicate that KCl premixing with other materials can solve agglomeration problems encountered during manufacturing processes as KCl-particle-particle interactions per unit volume are reduced.     

Application of the induction plasma to the synthesis of two dimensional steam methane reforming Ni/Al2O3 catalyst

The purpose of the study is to develop a new protocol for preparing supported two dimensional catalysts with high external and low internal surface by combining thermal plasma spraying and thermal plasma chemical vapour deposition (TPCVD) processes. The method was tested for the production of an Al₂O₃ supported Ni catalysts used for methane steam reforming. The deposition of catalytic materials is made in 2 successive steps. The first step deals with alumina powder sprayed by induction plasma spraying (IPS) on a molybdenum substrate. The experimental conditions have been turned towards γ-Al₂O_3. The second stage deals with the deposition of nickel at the nanometric scale on the alumina layer using the thermal plasma chemical vapour deposition method. This last step was focused on the study of the influence of the nozzle type employed for the nickel solution spraying, the reactor internal pressure, the concentration and the flow rate of nickel salts solution, Ni(NO₃)₂·6H₂O, on the catalyst response. The formulations were tested as methane steam reforming catalysts.The results demonstrate that the catalyst morphology depends on plasma projection conditions and show the effectiveness of combining IPS and TPCVD processes for producing catalysts in methane steam reforming.     

The oxidation of valeric acid in aqueous solution

The liquid phase oxidation of an aqueous solution of a lower fatty acid, valeric (pentanoic) acid, has been studied at high temperatures (240?325°C) and pressures (10.3-10.4 MPa) in a batch autoclave reactor. The objective of the study was to develop a mechanistic understanding of the wet oxidation of industrial wastewaters contaminated with vegetable oils. Valeric acid was chosen as the prototype molecule. High performance liquid chromatography (HPLC) has been used to identify the liquid products and estimate their concentrations as a function of the extent of oxidation. Moreover the technique of GC-MS has also been used to obtain information on specific intermediate oxidation products that could not be identified by HPLC. The gaseous products of the reaction have been also identified and quantified. A detailed reaction mechanism is proposed based on free radical reactions.