Synthesis of Biodiesel from Canola Oil Using Heterogeneous Base Catalyst

A series of alkali metal (Li, Na, K) promoted alkali earth oxides (CaO, BaO, MgO), as well as K₂CO₃ supported on alumina (Al₂O₃), were prepared and used as catalysts for transesterification of canola oil with methanol. Four catalysts such as K₂CO₃/Al₂O₃ and alkali metal (Li, Na, K) promoted BaO were effective for transesterification with >85 wt% of methyl esters. ICP-MS analysis revealed that leaching of barium in ester phase was too high (~1,000 ppm) when BaO based catalysts were used. As barium is highly toxic, these catalysts were not used further for transesterification of canola oil. Optimization of reaction conditions such as molar ratio of alcohol to oil (6:1–12:1), reaction temperature (40–60 °C) and catalyst loading (1–3 wt%) was performed for most efficient and environmentally friendly K₂CO₃/Al₂O₃ catalyst to maximize ester yield using response surface methodology (RSM). The RSM suggested that a molar ratio of alcohol to oil 11.48:1, a reaction temperature of 60 °C, and catalyst loading 3.16 wt% were optimum for the production of ester from canola oil. The predicted value of ester yield was 96.3 wt% in 2 h, which was in agreement with the experimental results within 1.28%.     

Transesterification in poly(ethylene terephthalate) and poly(ethylene naphthalate 2,6-dicarboxylate) blends: model compounds study

Kinetics of transesterification reaction in poly(ethylene terephthalate)-poly(ethylene naphthalate 2,6-dicarboxylate), PET-PEN, blends resulting from melt processing was simulated using model compounds of ethylene dibenzoate (BEB) and ethylene dinaphthoate (NEN). The exchange reaction between BEB and NEN was followed by ¹H NMR spectroscopy using signals from the aliphatic protons of ethylene glycol moieties at 4.66 and 4.78 ppm, respectively. The first-order kinetics was established under pseudo-first-order conditions for both reactants. Thus, the overall transesterification reaction was second order reversible. The reversibility was confirmed experimentally by heating a mixed sequence of 1-benzoate 2-naphthoate ethylene (BEN) under similar conditions. Both forward reaction of the equimolar amounts of the reagents and reverse reaction came to equilibrium at the same molar ratio of the reactants and reaction products of roughly 0.25:0.50:0.25 for BEB, BEN, and NEN, respectively. The rate equation for the transesterification reaction in the model system was modified using half-concentration of BEN, which is the only effective in the intermolecular exchange. Direct ester-ester exchange was deduced as a prevailing mechanism for the transesterification reaction under the conditions studied, and the values of equilibrium and rate constants, as well as other basic thermodynamic and kinetic parameters were determined. The use of Zn(OAc)₂ as a catalyst resulted in a significant decrease in the activation enthalpy of transesterification, which might be due to the partial switch of the reaction mechanism from primarily pseudo-homolytic to more heterolytic where Zn^II acts as a Lewis base which binds to the ester carbonyl oxygen.     

The role of Lewis bases on the improvement of the stereospecificity and activity of TiCl3/AlClEt2 catalyst system

Summary The effect of di-n-butyl ether (DBE) in the synthesis of a highly active propylene polymerization catalyst was studied. Electron-donors having ester and phosphate groups (ethyl benzoate-EB, diisobutyl phthalate-DIBP and tri-n-butyl phosphate-TBP) were added as second internal bases (IB₂) to the catalysts prepared by the reduction of TiCl₄ with AlClEt₂ (DEAC) in the presence of DBE as a first internal base (IB₁). The crystalline forms were examined for all catalyst samples by X-ray method. Special attention has been paid to the -TiCl₃ samples showing the best catalytic properties. These catalysts were evaluated in propylene polymerization in the absence and presence of external bases (EB, DIBP and DBE). The effects of internal and external bases on the catalyst activity and stereo-specificity are discussed.     

Classification of honeys by principal component analysis on the basis of chemical and physical parameters

Summary Eighteen chemical and physical parameters of nectar and honeydew honeys were determined and the results were analysed statistically by the method of principal component analysis. On the plots of principal component loadings, the honeys were divided into the following groups: (1) acacia honey; (2) rape honey; (3) linden, floral (nectar coming from various plants) and heather honeys; (4) honeydew honey. The samples which were a blend of nectar and honeydew honeys may be considered as a separate group between 3 and 4. The most important first principal component was strongly associated with the value of electrical conductivity, the contents of ash, free acids and proline, as well as with the pH and the diastase number. The principal component loadings and linear correlation suggested that these parameters contributed much more to the classification of honeys than apparent reducing sugars, apparent sucrose, mono-, di-, and trisaccharides, glucose and fructose. The classification of honeys by the method of principal component analysis may serve as an additional tool in specifying samples on the basis of their chemical composition.

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Klassifizierung von Honigen durch chemische und physikalische Parameter mit Hilfe der Hauptkomponentenanalyse

Zusammenfassung 18 chemische und physikalische Parameter der Nektar- und Honigtauhonige wurden bestimmt und die Ergebnisse statistisch mit Hilfe der Hauptkomponentenanalyse ausgewertet. Danach konnten die Honige in folgende Gruppen unterteilt werden: 1) Akazienhonige, 2) Rapshonige, 3) Linden-, Blüten-und Heidehonige, 4) Honigtauhonige. Zwischen dem Nektarhonig und Honigtauhonig lagen wahrscheinlich die Proben von Mischhonigen aus Blüten- und Waldtracht. Die bedeutendste erste Hauptkomponente war mit folgenden Parametern verbunden: elektrischer Leitfähigkeitswert und Aschegehalt, Gehalt an freien Säuren und Prolin sowie der pH-Wert und Diastasezahl. Aufgrund der Hauptkomponentenladungen und der linearen Korrelation kann angenommen werden, daß diese Parameter für die Honigklassifizierung von größerer Bedeutung sind als der Gehalt an reduzierenden Zuckern, scheinbarer Saccharose, Mono-, Di- und Trisaccharide, Glucose und Fructose. Die Klassifizierung der Honige mit Hilfe der Hauptkomponentenanalyse kann bei der Spezifikation einer Honigprobe aufgrund ihrer chemischen Zusammensetzung von Nutzen sein.

     

Mid‐infrared spectroscopy as a tool for real‐time monitoring of ethanol absorption in glycols

Fast, simple, accurate, and inexpensive methods for obtaining analyte concentration data are desirable in the industrial sector. In the present study, the use of Fourier transform mid‐infrared (FT‐MIR) spectroscopy, combined with partial least squares (PLS) regression, was investigated as a tool for real‐time monitoring of processes of ethanol absorption in glycols. Calibration was performed using simple synthetic samples containing ethanol, water, and monoethylene glycol (MEG) or diethylene glycol (DEG). The PLS models presented excellent performance, with correlation coefficients (R²) close to unity and root‐mean‐square errors of cross‐validation (RMSECV) and prediction (RMSEP) lower than 2% of the calibration data ranges for both analytes (ethanol and water) in both absorbents (MEG and DEG). The monitoring technique developed has potential to be applied in absorption processes and could also be used in other large‐scale unit operations, providing information in real time and enhancing process control.     

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.     

Thermal dehydrochlorination of pure PVC polymer: Part I—thermal degradation kinetics by thermogravimetric analysis

Thermal degradation of PVC occurs in two stages, with each stage subdivided into two substages. The first refers to the dehydrochlorination, where hydrochloric acid is formed, and giving polyene structures. Hitherto, the degradation mechanism and action of hydrochloric acid as a catalyst during the dehydrochlorination stage are poorly known. Recently, the importance of the tacticity has gained attention for its influence on the dehydrochlorination mechanism. The present work focused on the dehydrochlorination stage, studying the molecular structure by FTIR analysis and the kinetic parameters by TGA analysis in Nitrogen atmosphere, based on three mathematical methods: Friedman, Kissinger, and Flynn-Wall-Ozawa. The sample was a pure homopolymer obtained by suspension polymerization. The dehydrochlorination kinetics follows a first order reaction model and occurs by nucleation and growth. The dehydrochlorination begins with the loss of very labile chlorine atoms present in defective and isotactic molecular segments. The formed HCl acts as a catalyst in the degradation. Following 40% conversion, a drop in Ea is observed. After that, chlorine atoms present in syndiotactic and atactic sequences, are released and, added to the large number of polyene chain sequences, and an increase in Ea is observed up to 60% conversion, where the dehydrochlorination stage is concluded.     

The effect of adding devulcanized rubber on the thermomechanical properties of recycled polypropylene

This work aims to investigate the effect of adding vulcanized or partially devulcanized rubbers on recycled polypropylene (PPr), considering thermomechanical and morphological properties. The study proposes to better understand how structural changes underwent by rubber (after the devulcanization) contributed to improving the mechanical properties of the PPr. The PPr/rubber blends were prepared by a co-rotating twin-screw extruder and then were injected. The blends composed of the most devulcanized rubbers by microwaves with refined microstructure showed higher values of elongation at break and toughness. Data showed that the devulcanization process applied to the rubber interfered positively in its adhesion to the PPr. Data from dynamic mechanical analysis and atomic force microscopy indicated that the most devulcanized rubbers presented an interface more connected to PPr. These chemical interactions possibly impacted the mechanical properties of the PPr. Moreover, dilatation processes favored the fracture mechanisms of the PPr when rubber was added to it.     

Fast intra prediction algorithm based on texture analysis for 3D-HEVC encoders

The advances in display technologies and the growing popularity of 3D video systems have attracted more consumers for 3D viewing experiences, and, consequently, the demand for storage and transmission of 3D video content is increasing. To cope with this demand, a 3D video extension of high-efficiency video coding (HEVC) standard is being developed and near the final standardization stage. The upcoming 3D-HEVC standard is expected to provide higher encoding efficiency than its predecessors, supporting multiple views with high resolution, at a cost of considerable increase in computational complexity, which can be an obstacle to its use in real-time applications. This article proposes a novel complexity reduction algorithm developed to optimize the 3D-HEVC intra mode decision targeting real-time video processing for consumer devices with limited computational power, such as 3D camcorders and smartphones equipped with multiple cameras and depth acquisition capabilities. The proposed algorithm analyzes the texture frames and depth maps to estimate the orientation of edges present in the prediction unit data, speeding up the intra prediction process and reducing the 3D-HEVC encoding processing time. Experimental results demonstrate that the proposed algorithm can save 26 % in computational complexity on average with negligible loss of encoding efficiency. This solution contributes to make more feasible the compression of 3D videos targeting real-time applications in power-constrained devices.     

Synthesis of symmetric and asymmetric singly terminated elliptic ladder filters for multiplexing applications

An extension of the Cauer ladder development for synthesizing singly terminated filters with symmetric and asymmetric responses is presented. Basically, a driving‐point immittance including reactive constant elements is carried out in such a way that provides the transmission zeros. The reactive constant elements are introduced into the synthesis for two reasons. The first is to consider the possibility of the asymmetric position of transmission zeros in the real frequency axis. The second one is to obtain canonical forms, i.e. networks with the minimum number of elements in the case of symmetrical responses. To validate the proposed method, a filter with asymmetrical response has been synthesized, comparing different topologies for its use in multiplexers. This fact is illustrated with a Ku‐band elliptic response diplexer designed in H‐plane rectangular waveguide. © 2009 Wiley Periodicals, Inc. Int J RF and Microwave CAE, 2009.