Study of operating variables in the transformation of aqueous ethanol into hydrocarbons on an HZSM‐5 zeolite

With the aim of determining the possibilities of directly upgrading the liquid obtained from carbohydrate fermentation, the effect of operating conditions (temperature, space time, water content in the feed) has been studied in the catalytic transformation of aqueous ethanol into hydrocarbons on an HZSM‐5 zeolite in an isothermal fixed bed reactor. Special attention has been paid to the effect of water content on the yield, product distribution and catalyst deactivation. Although deactivation by coke decreases as the water content is increased, this content must be limited at 450 °C and higher temperatures in order to avoid irreversible deactivation of the catalyst by dealumination. © 2002 Society of Chemical Industry     

Mechanistic peculiarities of the N2O reduction by CH4 over Fe-silicalite

Transient isotopic studies in the temporal analysis of products (TAP) reactor evidenced the importance of the lifetime of oxygen species generated upon N₂O decomposition on extraframework iron sites of Fe-silicalite for methane oxidation at 723 K. Fe-silicalite effectively activates CH₄ when N₂O and CH₄ are pulsed together in the reactor. However, these oxygen species gradually become inactive for methane oxidation as the time delay between the N₂O and CH₄ pulses is increased from 0 to 2 s.     

Carbon nanotube supported ruthenium catalysts for the treatment of high strength wastewater with aniline using wet air oxidation

Multi-walled carbon nanotubes (MWCNT) can be efficiently used as support of ruthenium catalysts for the catalytic wet air oxidation of high strength wastewater containing aniline. Catalysts were prepared using different ruthenium precursors, Ruthenocene [Ru(η⁵-C₅H₅)₂], Ruthenium (1,5-cyclooctadiene, 1,3,5-cyclooctatriene) [Ru(cod)(cot)] and Ruthenium trichloride (RuCl₃ · xH₂O), different impregnation methods (excess solution and incipient wetness impregnation) and different MWCNT support surface chemistry (nitric acid oxidized MWCNT-COOH and Na₂CO₃ ion exchanged MWCNT-COONa). The efficiency of the aniline removal obtained with the catalysts prepared with different precursors decreases in the order [Ru(cod)(cot)] > RuCl₃ · xH₂O > [Ru(η⁵-C₅H₅)₂], 100% aniline conversion being obtained after 45 min of reaction with the catalyst prepared with [Ru(cod)(cot)]. The influence of the impregnation technique was found to be negligible, while the use of the MWCNT-COONa support led to increased catalyst performances when compared to that obtained with catalysts prepared with the MWCNT-COOH support. Leaching of ruthenium was observed in all cases, but the use of the precursor [Ru(cod)(cot)] and of the support MWCNT-COONa in the preparation of the catalysts seems to improve their stability. A direct relationship between metal load and catalyst stability was found and attributed to the strength of metal-support interactions.     

Prospects of N2O emission regulations in the European fertilizer industry

European authorities consider that N₂O emissions from nitric acid plants can be reduced to a large extent at a relatively low cost. Two regulation approaches can have major implications for the fertilizer industry in Europe. The EU integrated pollution prevention and control (IPPC) directive will be effective from October 2007 for existing plants. In this, emission permits will be based on best available techniques (BAT). Additionally, the EU commission will shortly consider whether the emission trading directive should be applicable to cover other greenhouse gases besides CO₂. This paper discusses advantages and drawbacks of these approaches, with emphasis on how emission trading with N₂O can be turned into a win–win situation both for European governments and for the fertilizer industry.     

The role of lanthana loading on the catalytic properties of Pd/Al2O3-La2O3 in the NO reduction with H2

The role of La₂O₃ loading in Pd/Al₂O₃-La₂O₃ prepared by sol–gel on the catalytic properties in the NO reduction with H₂ was studied. The catalysts were characterized by N₂ physisorption, temperature-programmed reduction, differential thermal analysis, temperature-programmed oxidation and temperature-programmed desorption of NO.

The physicochemical properties of Pd catalysts as well as the catalytic activity and selectivity are modified by La₂O₃ inclusion. The selectivity depends on the NO/H₂ molar ratio (GHSV = 72,000 h⁻¹) and the extent of interaction between Pd and La₂O₃. At NO/H₂ = 0.5, the catalysts show high N₂ selectivity (60–75%) at temperatures lower than 250 °C. For NO/H₂ = 1, the N₂ selectivity is almost 100% mainly for high temperatures, and even in the presence of 10% H₂O vapor. The high N₂ selectivity indicates a high capability of the catalysts to dissociate NO upon adsorption. This property is attributed to the creation of new adsorption sites through the formation of a surface PdO_x phase interacting with La₂O₃. The formation of this phase is favored by the spreading of PdO promoted by La₂O₃. DTA shows that the phase transformation takes place at temperatures of 280–350 °C, while TPO indicates that this phase transformation is related to the oxidation process of PdO: in the case of Pd/Al₂O₃ the O₂ uptake is consistent with the oxidation of PdO to PdO₂, and when La₂O₃ is present the O₂ uptake exceeds that amount (1.5 times). La₂O₃ in Pd catalysts promotes also the oxidation of Pd and dissociative adsorption of NO mainly at low temperatures (<250 °C) favoring the formation of N₂.     

CO2‐assisted polymer processing: A new alternative for intractable polymers

CO₂‐assisted polymer processing is proposed as an alternative route for intractable and high molecular weight polymers based on the plasticization effects of CO₂ and its direct effect on the melting behavior of semicrystalline polymers. A modified processing system was used to process a variety of polymers in the presence of high‐pressure CO₂. The system includes an extruder that was modified to allow for high pressures created by the injection of CO₂. The new design includes a modified feed section that allows a given mass of polymer to interact with CO₂ before and during the extrusion process. The inherent shear mixing and the presence of CO₂ allow for a specific control over the extrudate morphology. Results suggest that this alternative design provides a new and easy route to melt process high melt viscosity polymers of commercial importance, such as polytetrafluoroethylene (PTFE), fluorinated ethylene propylene copolymer (FEP), and syndiotactic polystyrene (s‐PS). The increased processability of these systems in CO₂ is related to the plasticization effect of CO₂ that was quantified through a depression in the glass‐transition temperature according to the Chow model. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1501–1511, 2004     

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.     

The Nyquist stability criterion in the Nichols chart

The Nyquist stability criterion is a widely used technique for determining in the complex s‐plane the stability of a dynamical system with feedback. This paper presents a practical and comprehensive method to compute the Nyquist stability criterion directly in the Nichols (magnitude/phase) chart. The proposed method also gives guidelines to design controllers to stabilize unstable plants when dealing with frequency domain techniques like the quantitative feedback theory robust control. Copyright © 2015 John Wiley & Sons, Ltd.