Isobutane/2-butene alkylation on MCM-22 catalyst. Influence of zeolite structure and acidity on activity and selectivity

The catalytic behavior of the novel MCM-22 zeolite for the continuous alkylation of isobutane with 2-butene has been investigated at a temperature of 50°C, 2.5 MPa total pressure, and a variety of olefin space velocities. At high olefin conversions the MCM-22 zeolite showed a very high initial cracking activity attributable to strong Brønsted acid sites, as well as to the existence of strong diffusional restrictions of the TMP's (formed inside the zeolite) to exit through the channels. At short times on stream (TOS), TMP's account for ca. 40% of the C₈ fraction. The olefin conversion and the cracking activity rapidly decline with TOS, while the alkylate product became richer in dimethylhexenes, indicating a predominance of 2-butene dimerization and a loss of hydrogen transfer activity as the catalyst aged. Moreover, MCM-22 gives less TMP's than large-pore zeolites (USY, beta, mordenite), but more than the mediumpore ZSM-5 at similar 2-butene conversion. The latter catalyst was much more selective for olefin dimerization than for isobutane alkylation, presumably because formation of the bulkier TMP's was strongly impeded in its smaller pores.     

Styrene-butadiene branched star-shaped asphalt modifiers: Synthesis and mechanical characterization

Abstract

The synthesis and the corresponding characterization of styrene-butadiene (SB), branched, star-shaped copolymers was investigated as part of a research project on asphalt modification using polymers with precise molecular structures. The method of anionic polymerization was followed to prepare samples of block copolymers of SB, a synthesis method that controls chain-architecture, molecular weight distribution, monomer distribution, and the average molecular weight. The research studies are the synthesis of block copolymers including linear, three- and four-arms constructs, depending on the coupling agent used. The techniques of nuclear magnetic resonance (1NMR), differential scanning calorimetry (DSC), gel permeation chromatography (GPC), and rheology were carried out to characterize the copolymers. From the results of the 1NMR, DSC, and GPC analyses, all star-shaped copolymers investigated showed a similar block copolymer composition. Furthermore, the rheological behavior of one of the synthesized star-shaped copolymers was nearly the same as a four-branched commercial copolymer. Rheologically, the four-arm block copolymer sample had the largest storage modulus (G′) among the branched copolymers synthetized, indicating that such architecture produces a highly structured material. In regard to polymer-modified asphalt formulations, the three-branched copolymer architecture yielded better elastic behavior than the four-branch version. In summary, the findings of this investigation provide new insight about a polymer system that may offer advantages in industrial asphalt paving applications.     

On reactive routing protocols in ZigBee wireless sensor networks

ZigBee is the primary standard solution for wireless sensor networks, implementing the Ad hoc On‐Demand Distance Vector (AODV) protocol in the network layer and supported by the standard IEEE 802.15.4. This study is focused on mesh topologies and the critical problems encountered when AODV is executed in conjunction with the Carrier Sense Multiple Access with Collision Avoidance protocol. These problems are mainly related to the packet overhead required to carry out route creation. To perform preliminary experiments to be able to implement AODV in a real network, a new metric is proposed herein. This metric uses fuzzy logic to help in the decision‐making process. The objective of the fuzzy routine is to determine, during the route‐discovery process, the best node to forward request/reply packets, with the aim of reducing packet overhead and energy consumption. Moreover, minor changes are also added to the discovery procedure of AODV to improve the performance of the route‐creation process. This intelligent version of AODV has provided promising experimental results, greatly reducing the number of packets required, with the consequent energy saving while selecting the best nodes to be part of the routes.     

Bayesian bivariate generalized Lindley model for survival data with a cure fraction

The cure fraction models have been widely used to analyze survival data in which a proportion of the individuals is not susceptible to the event of interest. In this article, we introduce a bivariate model for survival data with a cure fraction based on the three-parameter generalized Lindley distribution. The joint distribution of the survival times is obtained by using copula functions. We consider three types of copula function models, the Farlie–Gumbel–Morgenstern (FGM), Clayton and Gumbel–Barnett copulas. The model is implemented under a Bayesian framework, where the parameter estimation is based on Markov Chain Monte Carlo (MCMC) techniques. To illustrate the utility of the model, we consider an application to a real data set related to an invasive cervical cancer study.     

Event-driven,pattern-based methodology for cost-effective development of standardized personal health devices

Experiences applying standards in personal health devices (PHDs) show an inherent trade-off between interoperability and costs (in terms of processing load and development time). Therefore, reducing hardware and software costs as well as time-to-market is crucial for standards adoption. The ISO/IEEE11073 PHD family of standards (also referred to as X73PHD) provides interoperable communication between PHDs and aggregators. Nevertheless, the responsibility of achieving inexpensive implementations of X73PHD in limited resource microcontrollers falls directly on the developer. Hence, the authors previously presented a methodology based on patterns to implement X73-compliant PHDs into devices with low-voltage low-power constraints. That version was based on multitasking, which required additional features and resources. This paper therefore presents an event-driven evolution of the patterns-based methodology for cost-effective development of standardized PHDs. The results of comparing between the two versions showed that the mean values of decrease in memory consumption and cycles of latency are 11.59% and 45.95%, respectively. In addition, several enhancements in terms of cost-effectiveness and development time can be derived from the new version of the methodology. Therefore, the new approach could help in producing cost-effective X73-compliant PHDs, which in turn could foster the adoption of standards.     

Volatile Emissions Triggered by Multiple Herbivore Damage: Beet Armyworm and Whitefly Feeding on Cotton Plants

Plants are commonly attacked by more than one species of herbivore, potentially causing the induction of multiple, and possibly competing, plant defense systems. In the present paper, we determined the interaction between feeding by the phloem feeder silverleaf whitefly (SWF), Bemisia tabaci Gennadius (B-biotype = B. argentifolii Bellows and Perring), and the leaf-chewing beet armyworm (BAW), Spodoptera exigua Hübner, with regard to the induction of volatile compounds from cotton plants. Compared to undamaged control plants, infestation with SWF did not induce volatile emissions or affect the number and density of pigment glands that store volatile and nonvolatile terpenoid compounds, whereas infestation by BAW strongly induced plant volatile emission. When challenged by the two insect herbivores simultaneously, volatile emission was significantly less than for plants infested with only BAW. Our results suggest that tritrophic level interactions between cotton, BAW, and natural enemies of BAW, that are known to be mediated by plant volatile emissions, may be perturbed by simultaneous infestation by SWF. Possible mechanisms by which the presence of whiteflies may attenuate volatile emissions from caterpillar-damaged cotton plants are discussed.     

Antimony Solubility and Speciation in Aqueous Sulphuric Acid Solutions at 298 K

This work is an experimental and theoretical study of antimony speciation and the solubility of Sb₂O₅, Sb₂O₃ and Sb₂(SO₄)₃ at 298 K in aqueous sulphuric acid solutions (0 to 6 kmol/m³). A thermodynamic model was developed to quantify the solubility products and aqueous metal speciation. Main dissolved species were H₃SbO_3(aq) and H₃SbO_4(aq). The solubility of antimony increases with increasing solution acidity and with the presence of hydrogen peroxide in the solution. The following standard equilibrium constants at 298 K were obtained: Log K⁰_(Sb2O5) = 11.7±0.5, Log K⁰_(Sb2O3) = 32±1, and Log K⁰_(Sb2(SO4)3) = 55±2.     

Al ionic radius influence on molecular dynamics simulations ofγ-Al2O3

Molecular dynamics (MD) simulations of-Al₂O₃, using a pairwise additive interaction potential of Pauling's type with four different radii for aluminum atoms, were analysed in order to determine the influence of the radius on the modification of coordination numbers of A1 relative to the ideal structure, at two different temperatures of 300 and 1500 K. It is found that the best choice is the radius of penta-coordinated aluminum, reproducing structural and vibrational properties of the compound in excellent agreement with experimentally observed properties.     

The anodic oxidation of thiocyanate ion dissolved as KSCN in dimethylsulphoxide

The anodic oxidation of SCN⁻ ion dissolved as KSCN in dimethylsulphoxide, on platinum electrodes, was investigated at ca 25, 60 and 160°C by means of various non-stationary electrochemical techniques. At low temperatures one anodic and two main cathodic processes were found. The anodic oxidation of SCN⁻ ion yields as primary product the SCN radical, which readily produces (SCN)₂. The latter can be in part reduced back to SCN⁻ ion, because it reacts in part yielding solvated hydrogen ions which cause the second cathodic reaction. In the region of 60°C, no (SCN)₂ cathodic current is observed. In the region of 160°C the only reaction is SCN⁻ ion oxidation and the primary product polymerizes to (SCN)_x, which forms a film on the electrode, causing passivation.

On the basis of kinetic data obtained for the different reactions, a mechanism for the anodic oxidation of the SCN⁻ ion and for the passivating film formation is suggested. The second process only partly fits the Müller model for the electrochemical growth of insoluble layers.     

Digestibility and nutritional value of crude oil from three amaranth species

Oils from a selection ofAmaranthus caudatus, A. hypochondriacus andA. cruentus were extracted with hexane. The crude oils were analyzed for acid value, saponification and iodine number, and were included in basal casein diets for rat studies at 5 and 10% levels to replace equal amounts of refined cottonseed oil. The oils fromA. cruentus andA. hypochondriacus were similar in the oil properties studied and different fromA. caudatus. At either 5 or 10% food intake levels, weight gain and PER were not statistically different from values reported for cottonseed oil. True digestibility of amaranth oil was lower than that of cottonseed oil.A. cruentus oil gave the lowest digestibility. Oil levels induced statistical differences in food intake and digestibility. Oils fromA. caudatus, A. hypochondriacus and cottonseed induced similar serum cholesterol levels, while oil fromA. cruentus gave statistically higher values. Hemoglobin, hematocrit and serum proteins were similar among all groups. Microscopic analysis of the organs of the rats revealed some changes that were also found in cottonseed oil-fed rats. It was concluded that crude amaranth oil has lower digestibility than cottonseed oil, but that it is not responsible for growth-depressing effects when the seed is fed raw as compared to processed materials.