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.     

Inductive Model Generation for Text Classification Using a Bipartite Heterogeneous Network

Algorithms for numeric data classification have been applied for text classification. Usually the vector space model is used to represent text collections. The characteristics of this representation such as sparsity and high dimensionality sometimes impair the quality of general-purpose classifiers. Networks can be used to represent text collections, avoiding the high sparsity and allowing to model relationships among different objects that compose a text collection. Such network- based representations can improve the quality of the classification results. One of the simplest ways to represent textual collections by a network is through a bipartite heterogeneous network, which is composed of objects that represent the documents connected to objects that represent the terms. Heterogeneous bipartite networks do not require computation of similarities or relations among the objects and can be used to model any type of text collection. Due to the advantages of representing text collections through bipartite heterogeneous networks, in this article we present a text classifier which builds a classification model using the structure of a bipartite heterogeneous network. Such an algorithm, referred to as IMBHN （Inductive Model Based on Bipartite Heterogeneous Network）, induces a classification model assigning weights to objects that represent the terms for each class of the text collection. An empirical evaluation using a large amount of text collections from different domains shows that the proposed IMBHN algorithm produces significantly better results than k-NN, C4.5, SVM, and Naive Bayes algorithms.     

Controlling the phase stability of polymer blends through the introduction of impenetrable interfaces

In this work, the effect of the introduction of modified solid surfaces into polymer blends on the phase‐separation process was investigated. Glass fibers with surfaces having different chemistries were introduced into polystyrene–poly(methyl methacrylate) blends. The glass fibers used either had fully hydrated surfaces or had surfaces covered with a random copolymer, poly(styrene‐co‐methyl methacrylate). The copolymer was synthesized by free‐radical polymerization of styrene and methyl methacrylate in the presence of previously vinyl silane‐treated glass fibers. The copolymerization and grafting procedures were investigated by FTIR and thermal analysis. Blends containing the fibers were studied using FTIR microscopy and optical microscopy. FTIR microscopy results showed that the composition of the phases in the blends was shifted by using fibers with different surface chemistries. Fibers with grafted copolymers were capable of narrowing the immiscibility region in the phase diagram, while fully hydrated fibers were able to expand the gap. It was proposed that interfacial interactions regulated by a hydrophilic–hydrophobic type of forces were responsible for guiding the described phase‐separation process. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1619–1627, 2003     

Modification of porous copolymers network based on acrylonitrile

Summary The preparation of a chelating ion-exchange network based on acrylonitrile was carried out by chemical modification with hydroxylamine. The beads of resin were synthesized by aqueous suspension copolymerization of acrylonitrile (AN), styrene (STY) and divinylbenzene (DVB). The influence of diluent used in the suspension polymerization on the structure of the resulting copolymers was evaluated. The diluents employed were heptane (HEP), toluene (TOL) and anisole (ANI). It was found that the AN incorporation into copolymer structure was dependent on the diluent used. Conversion of nitrile groups into the amidoxime was conducted by treatment with hydroxylamine under alkaline solution. The resins were characterized by apparent density, surface area, average pore diameter, elemental analysis (CHN), FTIR and optical microscopy. Based on the results obtained, it was possible to control the porosity by diluent employed in the synthesis and to modify chemically a resin containing nitrile groups by hydroxylamine reaction. Received: 6 October 2001/Revised version: 2 April 2002/ Accepted: 11 April 2002     

Synthesis, characterization and crystal structure of a novel thiocyanate–ruthenium(II) complex

The cis-[Ru(dppb)(Me-bipy)(NCS)₂], dppb = 1,4-bis (diphenylphosphino)butane, Me-bipy = 4,4′-dimethyl-2,2′-bipyridine, and NCS = thiocyanate, was synthesized and characterized by spectroscopic and electrochemical techniques and its structure was determined by crystal X-ray analysis. The crystal structure reveals that the coordination geometry around the Ru(II) center is distorted octahedron where two molecules of thiocyanate are bonded to the ruthenium through nitrogen atom in cis orientation. The half-wave formal potential value E_1/2 = 0.8 V (versus Ag/AgCl) observed is considerable higher than that for the cis-[RuCl₂(dppb)(Me-bipy)] complex, E_1/2 = 0.6 V (versus Ag/AgCl), well illustrating the strong π-acceptor effect the NCS ligand toward the backbonding interaction with the Ru(II) metal center. The MLCT absorption bands of the thiocyanate complex present a higher molar absorptivity (about 12%) compared with the cis-[RuCl₂(dppb)(Me-bipy)] complex, in the same experimental conditions. These properties make the complex potentially promising for the photosensitization process.     

OpenCOPI: middleware integration for Ubiquitous Computing

In this paper, we present OpenCOPI (Open COntext Platform Integration), a Service-Oriented Architecture-based middleware platform that supports the integration of services provided by distinct sources, ranging from services offered by simple systems to more complex services provided by context-provision middleware. OpenCOPI offers selection and composition mechanisms to, respectively, select and compose services provided by different sources, considering applications of both Quality of Service and Quality of Context requirements. It also offers an adaptation mechanism that enables to adapt the application execution due to service failures, service quality fluctuation and user mobility. OpenCOPI allows the definition of applications in a higher abstraction level by the specification of a semantic workflow that contains abstract activities. This paper illustrates the use of OpenCOPI in an application from the Gas & Oil Industry and it also shows the evaluation of the main mechanisms of OpenCOPI: the service selection, composition, adaptation and workflow execution.     

Aromatization of [1-14C]heptane over “nonacidic” platinum-alumina catalyst

[1-¹⁴C]Heptane was aromatized under 5 atm pressure over a “nonacidic” 3% platinum on alumina catalyst maintained at 500 °C. The reactant was pumped in at a HLSV of 0.88, and the hydrogen-to-heptane mole ratio was 5.1. The samples of product were collected (one during the first 90 min and another during the next 90 min), the toluene was separated from the respective samples, and the radioactivity in each position of the toluene was determined by a degradation sequence. The distribution of radioactivity in sample 1 was as follows: in position 1–2.6%, 2–38.6%; 3–14.5%; 4–4.2%, and in the methyl group—40.1%. Approximately similar distribution of radioactivity was found in sample 2. 1,6-Ring closure is the most important pathway leading to the formation of toluene from [1-¹⁴C]heptane; lesser amounts of repetitive, 1,5-ring closure and hydrogenolysis, and bond shift reactions followed by 1,6-ring closure and dehydration can explain the distribution of radioactivity. The participation of 1,7-ring closure in the reaction is also indicated.     

The role of the Tm3+ concentration on CaMoO4 properties processed by microwave hydrothermal under stirring condition

The compounds based on calcium molybdate (CaMoO₄) are the subject of extensive research due to their excellent optical properties and a broad range of potential technological applications. In this work, we report a systematic study of CaMoO₄:Tm³⁺ phosphors synthesized by coprecipitation and processed in a microwave-hydrothermal system at low temperature (100°C) and stirring. The effect of the Tm³⁺ doping content (0%–12%) is studied in full detail to understand their role in the CaMoO₄:Tm³⁺ morphological, structural, and luminescent properties. The X-ray diffraction, Raman, and Fourier Transform Infrared spectroscopic techniques revealed that all the prepared powders have a tetragonal crystal structure with a distinct density of cation vacancies and structural disorders. The band gap remains almost constant for doping levels lower than 8%, but it narrows strongly for powders doped with 12% Tm³⁺ ions. The designed phosphors have shown two emission bands in which intensity depends on the Tm³⁺ ions doping level. For doping levels lower than 2%, the photoluminescence profile displays a broad emission band peaking at 543 nm (green). For concentrations higher than 4%, the band centered at 543 nm decreases in intensity and the near-infrared emission band at around 800 nm, assigned to ³F₃, ³H₄ → ³H₆ transitions from Tm³⁺ ion, become more intense. The outcomes of this work reveal that appropriated Tm³⁺ ions doping levels can be applied to suppress the PL emission in the visible range and improve that in the near-infrared region in CaMoO₄-based materials.     

Fabrication of hybrid proton-exchange membranes using a brandnew high temperature ionic liquid as charge transporting and clay modifier

The search for more compatibility between ionic liquids (ILs) and polymer matrices in proton-exchange membrane fuel cells (PEMFCs) is one of the ways in which IL leaking from proton-exchange membranes could be minimized. In this work, it is presented the synthesis of an aromatic high temperature ionic liquid (HTIL), which, incorporated into an aromatic matrix such as sulfonated polyether ether ketone (sPEEK), is expected to diminish the IL leaking that normally affects PEMFC. Phenylethylammonium trifluoromethane sulfonate (PhetaTfO) was successfully synthesized and characterized. Its melting point of 88°C makes it to classify as a HTIL and it was employed as modifier of natural Montmorillonite, forming the phenylethylammonium intercalated montmorillonite (MmtPheta) and thus, ternary membranes containing PhetaTfO, MmtPheta, and sPEEK were prepared and characterized. Immersion tests demonstrated a higher compatibility of PhetaTfO with matrix when compared to the reference DemaTfO, which was reflected in up to 30% lower IL loss by the synthesized IL than the DemaTfO; X-rays diffraction (XRD) patterns demonstrated that the modified clay was properly dispersed inside the membranes, while dynamic mechanical analyses (DMA) results indicated a strong plasticizer effect along the increase of PhetaTfO content inside the membrane, while at the same time, the conductivity increased in an exponential manner, which permitted to identify an empiric exponential equation to evaluate the effect of concentration on ionic conductivity. The maximum conductivity obtained at IL concentrations of around 38 wt% was 0.2 mS/cm. It could expect high ionic conductivities of 10 mS/cm when the concentration of this IL is 60%; nevertheless, in order to achieve that, crosslinking treatments should be done to give the membranes enough mechanical resistance.     

Poly(vinylidene fluoride) with zinc oxide and carbon nanotubes applied to pressure sheath layers in oil and gas pipelines

In this work, PVDF composites containing 0.2% (m/m) of carbon nanotubes (MWCNTs), PVDF with 5.0% (m/m) of zinc oxide (ZnO), and composites containing both particles in the same contents in the matrix were melt processed in a mini-extruder machine with double screws, using the counter-rotation mode. Composites were characterized by scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), X-ray diffraction (XRD), dynamic-mechanical analysis (DMA), and contact angle tests (CA). The samples presented the predominance of the α phase, with an increased degree of crystallinity as well as an increase in dimensional stability by incorporating both fillers, showing a synergistic effect between these particles, as shown on FTIR, DSC, and XRD results. SEM images showed a good dispersion of high aspect ratio particles. In general, DMA and TGA analysis showed that composites had not decreased their thermal and mechanical performance when compared to neat PVDF. Results of CA analysis showed an increase in the hydrophobicity of the sample containing MWCNTs. Permeability tests were also performed using a differential pressure system, combining high temperature and pressure, obtaining permeability measures and time lag. This work presents an alternative of composite materials, suggesting its application in the internal pressure sheath layers of oil and gas flexible pipes.