Coking kinetics of a Cr2O3/Al2O3 catalyst during 1-butene dehydrogenation: Effect of H2 partial pressure

The influence has been studied of the partial pressure of hydrogen (0–30 kPa) upon the coking rate of a Cr₂O₃/Al₂O₃ commercial catalyst during 1-butene dehydrogenation. Coke deposition has been analysed using a monolayer-multilayer reversible coke growth model (MMRC model). This model provides good fits to the experimental data, within the range of partial pressure of H₂ studied, and allows us to estimate the main kinetic parameters involved in the coking-deactivation process. The results obtained reveal a dual effect of hydrogen: competition against 1-butene for the active sites and the removal of coke precursors from the catalyst surface. Bom effects diminish the coking rate as the H₂ partial pressure is increased.     

The photooxidative gelation of cis-1,4- polybutadiene in solution

Irradiation of dilute solution of cis-1,4-polybutadiene in carbon tetrachloride with UV light in the presence of air causes fast formation of white precipitate—insoluble gel. It has been shown that carbon tetrachloride was effective photosensitizer for oxidation of cis-1,4-polybutadiene. Separated sol and gel fractions were analysed by infrared spectroscopy for better understanding of gelation process and structure of the gel. Three stages were detected in the process of oxidative photogelation of cis-1,4-polybutadiene in carbon tetrachloride solution: pre-gelation(sol-stage), gelation (sol/gel-stage) and post-gelation (gel-stage). In the first stage intensive photooxidative reactions between cis-1,4-polybutadiene, carbon tetrachloride and oxygen take place, giving products with high content of hydroperoxide and bounded chlorine. When hydroperoxide and chlorine content reached critical value, precipitation-gelation takes place. It is proposed sequence of free radical reactions which involves: photolysis of carbon tetrachloride to free radicals, addition of solvent radicals to the double bonds of rubber followed by combining of resulting radicals with oxigen to chlorinated polymeric peroxy radicals. Initially formed gel is peroxidic in nature, which photolyses to the more stabile ether gel by prolonged irradiation.     

The electrochemical reduction of nitrosonium ion in concentrated sulphuric acid: The NO/NO redox couple

The electrochemical reduction of NO⁺ ion in concentrated sulphuric acid has been studied on gold and platinum electrodes in the temperature range from 4·5 to 55·5°C with the rotating disk electrode, linear potential-sweep voltammetry and chronopotentiometry. On gold, NO⁺ is reduced to NO, the reaction being a reversible one-electron transfer reaction. The experimental diffusion coefficients of the NO⁺ ion and NO molecule are evaluated. On platinum, in the potential region where reduction of NO⁺ ion and oxidation of NO occur, oxides formed on the metal interfere, thus making the interpretation of the process difficult.     

The anodic oxidation of thiocyanate ion dissolved as KSCN in dimethylsulphoxide

The anodic oxidation of SCN⁻ ion dissolved as KSCN in dimethylsulphoxide, on platinum electrodes, was investigated at ca 25, 60 and 160°C by means of various non-stationary electrochemical techniques. At low temperatures one anodic and two main cathodic processes were found. The anodic oxidation of SCN⁻ ion yields as primary product the SCN radical, which readily produces (SCN)₂. The latter can be in part reduced back to SCN⁻ ion, because it reacts in part yielding solvated hydrogen ions which cause the second cathodic reaction. In the region of 60°C, no (SCN)₂ cathodic current is observed. In the region of 160°C the only reaction is SCN⁻ ion oxidation and the primary product polymerizes to (SCN)_x, which forms a film on the electrode, causing passivation.

On the basis of kinetic data obtained for the different reactions, a mechanism for the anodic oxidation of the SCN⁻ ion and for the passivating film formation is suggested. The second process only partly fits the Müller model for the electrochemical growth of insoluble layers.     

Quality assessment for a visual and automatic license plate recognition

Video transmission and analysis is often utilized in applications outside of the entertainment sector, and generally speaking this class of video is used to perform specific tasks. Examples of these applications include security and public safety. The Quality of Experience (QoE) concept for video content used for entertainment differs significantly from the QoE of surveillance video used for recognition tasks. This is because, in the latter case, the subjective satisfaction of the user depends on achieving a given functionality. Recognizing the growing importance of video in delivering a range of public safety services, we focused on developing critical quality thresholds in license plate recognition tasks based on videos streamed in constrained networking conditions. Since the number of surveillance cameras is still growing it is obvious that automatic systems will be used to do the tasks. Therefore, the presented research includes also analysis of automatic recognition algorithms.     

A new set distance and its application to shape registration

We propose a new distance measure, called Complement weighted sum of minimal distances, between finite sets in ${\mathbb Z }^n$ and evaluate its usefulness for shape registration and matching. In this set distance the contribution of each point of each set is weighted according to its distance to the complement of the set. In this way, outliers and noise contribute less to the new similarity measure. We evaluate the performance of the new set distance for registration of shapes in binary images and compare it to a number of often used set distances found in the literature. The most extensive evaluation uses a set of synthetic 2D images. We also show three examples of real problems: registering a set of 2D images extracted from synchrotron radiation micro-computed tomography (SR $\upmu $ CT) volumes depicting bone implants; the difficult multi-modal registration task of finding the exact location of a 2D slice of a bone implant, as imaged by a light microscope, within a 3D SR $\upmu $ CT volume of the same implant; and finally recognition of handwritten characters. The evaluation shows that our new set distance performs well for all tasks and outperforms the other observed distance measures in most cases. It is therefore useful in many image registration and shape comparison tasks.     

A genetic algorithm for job-shop scheduling with operators enhanced by weak Lamarckian evolution and search space narrowing

The job-shop scheduling problem with operators is a very interesting problem that generalizes the classic job-shop problem in such a way that an operation must be algorithm to solve this problem considering makespan minimization. The genetic algorithm uses permutations with repetition to encode chromosomes and a schedule generation scheme, termed OG&T, as decoding algorithm. This combination guaranties that at least one of the chromosomes represents and optimal schedule and, at the samhat machines and operators are idle while an operation is available to be processed. To improve the quality of the schedules for large instances, we use Lamarckian evolution and modify the OG&T algorithm to further reduce the idle time of the machines and operators, in this case at the risk of leaving all optimal schedules out of the search space. We conducted a large experimental study showing that these improvements allow the genetic algorithm to reach high quality solutions in very short time, and so it is quite competitive with the current state-of-the-art methods.     

Enantiospecific synthesis of (R)-1,7-dioxaspiro [5.5]undecane [major component of olive fruit fly (Dacus Oleae) sex pheromone] from d-Fructose

The synthesis of the title compound13 has been carried out through the preparation of its precursor, (3R,4R,5S,6R)-3,4,5-trihydroxy-1,7-dioxaspiro[5.5]undecane (6), obtained fromd-fructose using Wittig's methodology, reduction, and spiroketalation. Compound6 was transformed into13 by a Barton deoxygenation at C-5 followed by a Corey dideoxygenation at C-3,4 of the appropriately protected derivatives.Enantiospecific synthesis of spiroacetals. Part II. For Part I, see Izquierdo and Plaza (1990).     

Invariant‐set‐based fault diagnosis in Lure systems

In this paper, we present an invariant‐set‐based method for actuator and sensor fault detection and isolation in Lure systems. The Lure plant is controlled by an observer‐based feedback tracking controller, designed for the nominal (fault‐free) system. Suitable residual signals are constructed from measurable system outputs and estimates associated with the nominal observer. Faults are diagnosed by online contrasting the residual signal trajectories against sets of values that the residuals are shown to attain under healthy or faulty operation. These values are obtained via set‐invariance analysis of the system closed‐loop trajectories. Copyright © 2013 John Wiley & Sons, Ltd.