Catalysts based in cerium oxide for wet oxidation of acrylic acid in the prevention of environmental risks

Acrylic acid is a refractory compound for the non-catalytic wet oxidation (WO) process and can seriously damage the environment when released in industrial effluents. Oxidation of acrylic acid by catalytic wet oxidation (CWO) was studied in slurry conditions in a high-pressure batch reactor at 200 °C and 15 bar of oxygen partial pressure. Several solid cerium-based catalysts prepared in our laboratory were used (Ag/Ce, Co/Ce, Mn/Ce, CeO, MnO) and evaluated in terms of activity, selectivity and stability. Mn/Ce shows the higher activity in 2 h with 97.7% reduction of total organic carbon (TOC) followed by: MnO(95.5%)>Ag/Ce(85.0%)>Co/Ce(65.1%)>CeO(61.2%). Attempts were also carried out to analyze the influence of different Mn/Ce molar ratios. High percentages of Mn lead to practically total organic carbon concentration (TOC) abatements while low ratios lead to the formation of non-oxidizable compounds. Acrylic acid was readily degraded by all the catalysts pointing out the high importance of using a catalytic process. pH was an indicator of the reaction pathway and acetic acid was found as the major reaction intermediate compound; however it is completely oxidized after 2 h with exception for Co/Ce, CeO and MnO. Carbon adsorption and leaching of metals were poorly found for Mn/Ce indicating high stability. The catalyst microstructure after the reaction was analyzed and formation of whiskers of β-MnO₂ (or less probably MnOOH) were observed at the catalyst surface. Therefore, Mn/Ce revealed to be a promising catalyst for the treatment of effluents containing acrylic acid; nevertheless, its commercialization depends on further research.     

Substrate-mediated interactions and intermolecular forces between molecules adsorbed on surfaces

Adsorbate interactions and reactions on metal surfaces have been investigated using scanning tunneling microscopy. The manners in which adsorbates perturb the surface electronic structure in their vicinity are discussed. The effects these perturbations have on other molecules are shown to be important in overlayer growth. Interactions of molecules with surface steps are addressed, and each molecule's electron affinity is shown to dictate its adsorption sites at step edges. Standing waves emanating from steps are demonstrated to effect transient molecular adsorption up to 40 A away from the step edge. Halobenzene derivatives are used to demonstrate how the surface is important in aligning reactive intermediates.     

Produkte der Dimerisierung ungesättigter Fettsäuren IX: Kinetische Untersuchungen zur Dimerisierung von Linolsäure

Products of the Dimerisation of Unsaturated Fatty Acids IX: Kinetic Studies about the Dimerisation of Linoleic Acid To clarify the dimerisation process of linoleic acid, we investigated samples taken in different time intervals. The first reaction step is a water addition at double bonds of the starting material and not double bond isomerisation as previously assumed. The resulting unsaturated monohydroxy fatty acids can cyclize with the second double bond in an intramolecular reaction forming 2,5-disubstituted tetrahydrofuran respectively 2,6-disubstituted tetrahydropyran derivates. Linolenic acid, present nearly always in small amounts in linoleic acid, reacts to first dimerisation products with linoleic acid by formation of a C-C-bond. The aliphatic dimers cyclize in an intramolecular reaction to mono-cyclic compounds. No dimeric acids, which would result from a Diels-Alder-reaction, could be identified. Bicyclic and aromatic dimeric acids can also be found in the early phase of the dimerisation. In the further progress of the reaction isomerisations, hydrogenations and dehydrogenations of the primary reaction products occur, thus the content of aromatic substances increases steadily.     

Modelling formation and growth of H2SO4-H2O aerosols: Uncertainty analysis and experimental evaluation

An aerosol dynamics model, AERO2, is presented, which describes the formation of H₂SO₄-H₂O aerosol in a smog chamber. The model is used to analyse how the uncertainties on four input parameters are propagated through an aerosol dynamics model. The input parameters are: the rate of the reaction between SO₂ and OH (k₁), the ratio between the nucleation rate used in AERO2 and that derived from classical nucleation theory (t_n), the H₂SO₄ mass accommodation coefficient () and a measure of the turbulence intensity in the reactor (k_e). Uncertainties for these parameters are taken from the literature. One of the results of the analysis is that AERO2 and aerosol dynamics models in general can only predict upper bounds for the total number (N_tot) and total volume (V_tot) concentrations of the particles. The uncertainties on N_tot and V_tot are mainly due to the uncertainties on k₁, and t_n. An uncertainty factor of 20–100 still remains when the uncertainty on k₁, is reduced to ±5%. Aerosol measurements from three smog chamber experiments have therefore been used, in an attempt to reduce the uncertainty on k₁ and t_n. Values for k₁ are obtained in the reduced range 7.8 × 10⁻¹³ to 1.0 × 10⁻¹² cm³ s⁻¹, which is within the range found in the literature. For t_n, values in the range 10⁴–10⁷ are obtained, which is close to the upper bound of the range in literature. These values for t_n are in marked contrast with a recent set of experiments on nucleation in H₂SO₄-H₂O mixtures, which suggests a value for t_n of at most 10⁻⁵.     

Investigations of ZnO thin films deposited by a reactive pulsed laser ablation

Highly transparent ZnO thin films were deposited at different substrate temperatures by pulsed laser deposition in an oxygen atmosphere. The thin films were characterized by various techniques including X-ray diffraction, scanning electron microscopy, optical absorption, and photoluminescence. We demonstrated that oriented wurtzite ZnO thin films could be deposited at room temperature using a high purity zinc target. Variable temperature photoluminescence revealed new characteristics in the band edge emission. The underlying mechanism for the observed phenomena was also discussed.     

A globally asymptotically stabilizing trajectory tracking controller for fully actuated rigid bodies using landmark‐based information

In this paper, we address the problem of designing a control law based on sensor measurements that provides global asymptotic stabilization to a reference trajectory defined on the . The proposed control law is a function of the angular velocity, of vector measurements characterizing the position of some given landmarks, and of their rate of change. We provide sufficient conditions for the existence of synergistic potential functions on SO(3) which are pivotal in the generation of a suitable hybrid control law. We also provide sufficient conditions on the geometry of the landmarks to solve the given problem. Finally, the proposed solution is simulated and compared with a continuous feedback control law. Copyright © 2014 John Wiley & Sons, Ltd.     

Impact of white-matter mask selection on DTI histogram-based metrics as potential biomarkers in cerebral small vessel disease

Magnetic Resonance Materials in Physics, Biology and Medicine - Histogram-based metrics extracted from diffusion-tensor imaging (DTI) have been suggested as potential biomarkers for cerebral small...     

On the design of multi‐rate tracking controllers: Application to rotorcraft guidance and control

This paper presents a new methodology for the design and implementation of gain‐scheduled controllers for multi‐rate systems. The proposed methodology provides a natural way to address the integrated guidance and control problem for autonomous vehicles when the outputs are sampled at different instants of time. A controller structure is first proposed for the regulation of non‐square multi‐rate systems with more measured outputs than inputs. Based on this structure, an implementation for a gain‐scheduled controller is obtained that satisfies an important property known as the linearization property. The implementation resembles the velocity implementation for single‐rate systems. The method is then applied to the problem of steering an autonomous rotorcraft along a predefined trajectory defined in terms of space and time coordinates. By considering a convenient error vector to describe the vehicle's dynamics, the trajectory tracking problem is reduced to that of regulating the error variables to zero. Because of the periodic multi‐rate nature of the onboard sensor suite, the controller synthesis is dealt with under the scope of linear periodic systems theory. Simulation results obtained with a full non‐linear rotorcraft dynamic model are presented and discussed. Copyright © 2010 John Wiley & Sons, Ltd.     

Video Surveillance Online Repository (ViSOR): an integrated framework

The availability of new techniques and tools for Video Surveillance and the capability of storing huge amounts of visual data acquired by hundreds of cameras every day call for a convergence between pattern recognition, computer vision and multimedia paradigms. A clear need for this convergence is shown by new research projects which attempt to exploit both ontology-based retrieval and video analysis techniques also in the field of surveillance. This paper presents the ViSOR (Video Surveillance Online Repository) framework, designed with the aim of establishing an open platform for collecting, annotating, retrieving, and sharing surveillance videos, as well as evaluating the performance of automatic surveillance systems. Annotations are based on a reference ontology which has been defined integrating hundreds of concepts, some of them coming from the LSCOM and MediaMill ontologies. A new annotation classification schema is also provided, which is aimed at identifying the spatial, temporal and domain detail level used. The ViSOR web interface allows video browsing, querying by annotated concepts or by keywords, compressed video previewing, media downloading and uploading. Finally, ViSOR includes a performance evaluation desk which can be used to compare different annotations.