Kinetic analysis of the complex process of poly(vinyl alcohol) pyrolysis using a new coupled peak deconvolution method

A peak deconvolution procedure used for the analysis of data corresponding to simultaneous overlapping processes begins with separation of individual processes using functions such as Gaussian, Lorentzian, Weibull, and Fraser–Suzuki (FS) followed by application of kinetic analysis methods to the separated peaks. We propose a coupled peak deconvolution procedure to link the parameters of the FS functions of similar peaks in two DTG curves obtained at different linear heating rates, so that the coordinates of each peak can be obtained in a constrained manner. The proposed technique is a kinetic deconvolution method rather than a pure mathematical deconvolution technique. To analyze individual peaks in our study, the non-parametric kinetic and Freidman’s isoconversional methods have been applied to determine kinetic triplet of each process. This technique has been tested with both simulated and experimental data. Using this technique, the effects of molecular weight and degree of hydrolysis of polyvinyl alcohol (PVA) samples on reaction mechanism and activation energy of thermal degradation were studied. The presence of acetate group in the PVA samples causes thermal stability, decreases the rate of main reactions, and increases the activation energy. The results of this study may help tailor heat-resistant materials with proper choice of polymer characteristics.     

Developing Thermodynamic Micellization Approach to Model Asphaltene Precipitation Behavior

An little known yet significant issue in petroleum production processes in petroleum reservoirs is asphaltene precipitation/deposition. Asphaltene has not only a fuzzy and vague nature but it also can cause detrimental problems like reservoir blockage and, as a result, low oil recovery. To tackle this issue, many researchers have attempted to monitor asphaltene behavior versus thermodynamic conditions. A thermodynamic micellization approach is implemented in this work to describe asphaltene precipitation behavior for two sample fluids from Iranian reservoirs. First, the basic structures of the addressed approach and different contributions to Gibbs free energy of micellization proposed by Victorov and Firoozabadi (VF) are demonstrated. Second, a detailed sensitivity analysis with respect to the model parameters is performed by utilizing a new calculation strategy. Finally, a comparison between the predicted precipitation curve and the experimental one is illustrated; moreover, comparing our results with those reported by Victorov proves the superiority of the new strategy over the conventional one. The significance of this study shows the effect of each micellization parameter on the asphaltene precipitation behavior curve and illustrates the ability of the micellization approach evolved by VF in monitoring the effect of pressure on asphaltene precipitation using the new calculation procedure. Outcomes from this study could couple with commercial reservoir simulation software to improve precision and integrity for designing robust and effective production units.     

CH4 reforming with CO2 for syngas production over La2O3 promoted Ni catalysts supported on mesoporous nanostructured γ-A12O3

Nanostructured -y-A12O3 with high surface area and mesoporous structure was synthesized by sol-gel method and employed as catalyst support for nickel catalysts in methane reforming with carbon dioxide. The prepared samples were characterized by XRD, N2 adsorption-desorption, TPR, TPO, TPH, NH3-TPD and SEM techniques. The BET analysis showed a high surface area of 204 m2.g-1 and a narrow pore-size distribution centered at a diameter of 5.5 nm for catalyst support. The BET results revealed that addition of lanthanum oxide to aluminum oxide decreased the specific surface area. In addition, TPR results showed that addition of lanthanum oxide increased the reducibility of nickel catalyst. The catalytic evaluation results showed an increase in methane conversion with increasing lanthanum oxide to 3 mol% and further increase in lanthanum content decreased the catalytic activity. TPO analysis revealed that the coke deposition decreased with increasing lanthanum oxide to 3 mol%. SEM and TPH analyses confirmed the formation of whisker type carbon over the spent catalysts. Addition of steam and Oxide to drv reformin feed increased the methane conversion and led to carbon free ooeration in combined orocesses.     

Nanostructured polypyrrole for automated and electrochemically controlled in-tube solid-phase microextraction of cationic nitrogen compounds

The authors describe an efficient method for microextraction and preconcentration of trace quantities of cationic nitrogen compounds, specifically of anilines. It relies on a combination of electrochemically controlled solid-phase microextraction and on-line in-tube solid-phase microextraction (SPME) using polypyrrole-coated capillaries. Nanostructured polypyrrole was electrically deposited on the inner surface of a stainless steel tube and used as the extraction phase. It also acts as a polypyrrole electrode that was used as a cation exchanger, and a platinum electrode that was used as the anode. The solution to be extracted is passed over the inner surface of the polypyrrole electrode, upon which cations are extracted by applying a negative potential under flow conditions. This method represents an ideal technique for SPME of protonated anilines because it is fast, easily automated, solvent-free, and inexpensive. Under optimal conditions, the limits of detection are in the 0.10–0.30 μg L‾¹ range. The method works in the 0.10 to 300 μg L‾¹ concentration range. The inter- and intra-assay precisions (RSD%; for n = 3) range from 5.1 to 7.5 % and from 4.7 to 6.0 % at the concentration levels of 2, 10 and 20 μg L‾¹, respectively. The EC-in-tube SPME method was successfully applied to the analysis of methyl-, 4-chloro-, 3-chloro and 3,4-dichloroanilines in (spiked) water samples.

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Propane-1,2,3-triyl tris(hydrogen sulfate): A mild and effcient recyclable catalyst for the synthesis of biscoumarin derivatives in water and solvent-free conditions简

A simple, efficient, and ecofriendly procedure has been developed using propane-l,2,3-triyl tris（hydrogen sulfate） as a catalyst for the synthesis of biscoumarin derivatives in water and solvent-free conditions. The significant features of the present protocol are simplicity, environmentally benign, high yields, no chromatographic separation, and recyclability of the catalyst.     

Fabrication of Electrochemical Sensor Based on CeO2−SnO2 Nanocomposite Loaded on Pd Support for Determination of Nitrite at Trace Levels

Here, an electrochemical sensor based on CeO₂‐SnO₂/Pd was prepared and used for highly selective and sensitive determination of nitrite in some real samples. This nanocomposite was characterized by various methods like X‐ray photoelectron spectroscopy, X‐ray diffraction, energy dispersive spectroscopy, Fourier‐transform infrared spectroscopy, field emission scanning electron microscopy, and transmission electron microscopy. The electrochemical behavior of the sensor was evaluated by cyclic voltammetry. The results showed excellent catalytic property of the nanocomposite as a an electrocatalyst for nitrite oxidation. In the following, the experimental parameters affecting the analytical signal for nitrite were optimized. Under the optimal conditions, the limit of detection and sensitivity of the sensor were calculated as 0.10 μM and 652.95 μA.mM^?1.cm^?2, respectively. Also, the response of the sensor was linear in the range of 0.36 to 2200 μM of nitrite. Finally, some of the inherent features of the sensor such as repeatability, reproducibility and stability were examined after evaluation of the sensor selectivity in the presence of several interfering species.     

Kinetic Isotope Effect as a Tool To Investigate the Oxygen Reduction Reaction on Pt-based Electrocatalysts – Part II: Effect of Platinum Dispersion

We investigated the oxygen reduction reaction (ORR) mechanism on Pt nanoparticles (NPs) dispersed on several carbon blacks with various physicochemical properties (i. e. specific surface ranging from 80 to 900 m² g⁻¹, different graphitization degree, etc.). Using the kinetic isotope effect (KIE) along with various electrochemical characterizations, we determined that the rate determining step (RDS) of the ORR is a proton-independent step when the density of Pt NPs on the surface of the carbon support is high. Upon decrease of the density of Pt NPs on the surface, the RDS of the ORR starts involving a proton, as denoted by an increase of the KIE >1. This underlined the critical role played by the carbon support in the oxygen reduction reaction electrocatalysis by Pt supported on high surface area carbon.     

Synthesis, characterization and properties of novel thermally stable poly(urethane-oxazolidone) elastomers

Oxazolidone-incorporated polyurethane elastomers based on hydroxyl terminated polycaprolactone, were synthesized and characterized. Reaction of epoxy-terminated polyurethane with isocyanate librated from a blocked polyisocyanate was the strategy followed. The reaction condition was optimized through preparation of model oxazolidones. Epoxy-terminated polyurethanes were prepared from reaction of glycidol with NCO-terminated polyurethane prepolymers and curing agent was synthesized from the reaction of trimethylol propane, toluene diisocyanate and N-methyl-aniline. Incorporation of heterocyclic oxazolidone groups into the polyurethane backbone caused improvements in thermal and mechanical properties. Investigation of structure-property relationship for prepared elastomers showed that the main determining factors for observed properties were crosslink density, crystallinity and content of oxazolidone rings.