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.     

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.     

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.     

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.     

Soft computing and cooperative strategies for optimization

In the last years, metaheuristics have emerged as powerful algorithmic approaches which have been applied with great success to difficult combinatorial optimization problems. However, this does not mean that metaheuristics can be applied blindly to any new problem.In this contribution we showed how the most basic ingredients of Soft Computing, namely fuzzy sets and fuzzy rules, are used in the context of a simple metaheuristic and a cooperative strategy based on it, to obtain successful results for the p-median problem.     

Analysis of the inappropriate utilization of the emergency service of a third-level hospital

OBJECTIVE: a) To find the reasons for inadequate use of Hospital Casualty Departments (HCDs); b) to discover the general population's levels of information concerning non-hospital Emergency Services (NESs); c) to analyse the relationship between the type of Primary Care Centre (PCC), i.e. whether reformed or not, and inadequate use of HCDs. DESIGN: A crossover study. SETTING: The Germans Trias i Pujol Hospital Casualty Department, Badalona. PATIENTS: A random sample of 321 patients over 14 years old, who were attended for pathologies considered emergencies not requiring hospital treatment. MEASUREMENTS AND MAIN RESULTS: The variables gathered were: age, gender, where the patient came from, reason for hospital use, knowledge of NESs and subsequent referral. 83.2% of patients attended on their own initiative. The main reasons given were "advantages of a hospital" and "the persistence of symptoms." 49% of the patients stated they knew of the NESs. 80% of the patients proceeded from PCCs which had not been reformed. There were no statistically significant differences (p > 0.05) when the variables "reason for use" and "knowledge of NESs" were compared in relation to where the patient came from (i.e. reformed or non-reformed PCC). CONCLUSIONS: General practitioners in reformed PCCs are less likely to refer to HCDs. Knowledge and use of NESs should be actively supported.     

Dynamic fatigue behaviour of a steatite ceramic

Dynamic fatigue of a low dielectric loss steatite was investigated. To this end, the values of n and B, the so‐called subcritical crack growth (SCG) parameters were experimentally determined. The steatite exhibited the expected dynamic fatigue behaviour, so that the stress corrosion susceptibility parameter, n, of 24 was obtained. In addition, the material/environment parameter B, which is a constant for a given test environment, was also attained. These parameters are instrumental in predicting the lifetime of components under stress. When the applied load is such that the resulting strength equals half of the inert strength (σ_i), defined as the strength of a sample tested in an inert environment or at a fast stress rate, i.e. where no subcritical crack growth occurs, the time to failure (t_f) of the material was found to be ～140 h. Measurement of the fracture toughness of steatite is also of upmost importance and so it was determined using three test methods. A value of K_Ic = 1.91 ± 0.29 MPa m^1/2 was attained by the indentation fracture method through measurement of the cracks emanating from the Vickers indentation. This value is in good agreement with those determined using the K_Isc (surface crack in flexure) test method (2.21 ± 0.07 MPa m^1/2) and fractography analysis test method (2.00 ± 0.44 MPa m^1/2). Differences in test procedure and analysis causing the values from each test method to be different are discussed.     

Solving identity delegation problem in the e-government environment

At present, many countries allow citizens or entities to interact with the government outside the telematic environment through a legal representative who is granted powers of representation. However, if the interaction takes place through the Internet, only primitive mechanisms of representation are available, and these are mainly based on non-dynamic offline processes that do not enable quick and easy identity delegation. This paper proposes a system of dynamic delegation of identity between two generic entities that can solve the problem of delegated access to the telematic services provided by public authorities. The solution herein is based on the generation of a delegation token created from a proxy certificate that allows the delegating entity to delegate identity to another on the basis of a subset of its attributes as delegator, while also establishing in the delegation token itself restrictions on the services accessible to the delegated entity and the validity period of delegation. Further, the paper presents the mechanisms needed to either revoke a delegation token or to check whether a delegation token has been revoked. Implications for theory and practice and suggestions for future research are discussed.