Catalytic effect of MCM-41 in the pyrolysis of tobacco and several substances used as additives in the preparation of commercial cigarettes

Comunicación presentada en forma de póster en el "12th Mediterranean Congress of Chemical Engineering", Barcelona (Spain), November 15-18, 2011.

Kinetic study of thermal 1,3-dipolar cycloaddition of azomethine ylides using differential scanning calorimetry as monitoring window

Kinetics of 1,3-dipolar cycloaddition involving azomethine ylides, generated from thermal [1,2]-prototropy of the corresponding imino ester, employing differential scanning calorimetry (DSC), is surveyed. Glycine and phenylalanine derived imino esters have different behavior. The first one prefers reacting with itself at 75 ºC, rather than with the dipolarophile. However, the α-substituted imino ester gives the cycloadduct at higher temperatures. The thermal dynamic analysis by 1H NMR of the neat reaction mixture of the glycine derivative reveals the presence of signals corresponding to the dipole in very small proportion. The non-isothermal and isothermal DSC curves of the cycloaddition of phenylalaninate and diisobutyl fumarate are obtained from freshly prepared samples. The application of known kinetic models and mathematical multiple non-linear regressions (NLR) allow to determine and to compare Ea, lnA, reaction orders, and reaction enthalpy. Finally a rate equation for each different temperature can be established for this particular thermal cycloaddition.

Extinction trends of threatened invertebrates in peninsular Spain

Using information from two recently published atlases of threatened invertebrate species in peninsular Spain, we examined the climatic, land use and geographic characteristics of the 100 km2 UTM cells with most likelihood of suffering extinctions (extinction cells), as well as the attributes of the species prone to population extinctions. Extinction cells have had significantly (1) lower precipitation values, (2) higher temperatures, (3) higher percentages of anthropic land uses or (4) higher rates of anthropization during the last 20 years than the remaining cells. Nevertheless, probable extinctions may occur under a wide range of climatic and anthropization change rates and these variables can only explain a low proportion (~5 %) of variability in the occurrence or number of extinction cells. Aquatic species seem to suffer higher local extinction rates than terrestrial species. Interestingly, many invertebrate species with approximately 25 or less occurrence cells are on a clear trajectory towards extinction. These results outline the difficulties and uncertainties in relating probable population extinctions with climatic and land use changes in the case of invertebrate data. However, they also suggest that a third of the considered Spanish threatened species could have lost some of their populations, and that current conservation efforts are insufficient to reverse this tendency.

Análisis experimental de la pérdida de adherencia hormigón-acero en hormigones sometidos a altas temperaturas

En el conjunto de materiales de construcción habituales en la edificación y las obras de ingeniería, el hormigón destaca entre otras razones por su excelente comportamiento frente a las altas temperaturas y la exposición al fuego. El presente estudio se centra en la adherencia residual entre el hormigón y las barras de acero corrugado soldable tras exponer probetas a altas temperaturas y enfriarlas hasta temperatura ambiente por convección natural. El estudio incluye hormigones de resistencia convencional, hormigones de alta resistencia y hormigones reforzados con fibras de polipropileno y fibras de acero. La adherencia hormigón-acero se ha medido mediante el conocido ensayo de pull-out. La campaña experimental también ha incluido la resistencia a compresión y la resistencia a tracción indirecta. Parte de las probetas se han ensayado a 28 días de edad a temperatura ambiente. A 60 días de edad se han repetido los ensayos a temperatura ambiente y se han realizado esos mismos ensayos en probetas calentadas en un horno industrial hasta tres rangos de temperatura: 450°C, 650°C y 825°C. Previo al proceso de calentamiento han sido sometidas durante 3 horas a un escalón de secado a 120°C. Mediante la metodología propuesta ha sido posible caracterizar la evolución de la pérdida de adherencia residual entre el acero y el hormigón conforme se exponen los especímenes a temperaturas más elevadas. La adición de fibras no tiene una influencia clara en la adherencia a temperatura ambiente. Sin embargo, sí se ha conseguido determinar una mejora sustancial de la adherencia residual en los hormigones, reforzados con fibras de acero sometidos a altas temperaturas.

Raman spectroscopy study of the transformation of the carbonaceous skeleton of a polymer-based nanoporous carbon along the thermal annealing pathway

We report a multi-wavelength Raman spectroscopy study of the structural changes along the thermal annealing pathway of a poly(furfuryl alcohol) (PFA) derived nanoporous carbon (NPC). The Raman spectra were deconvoluted utilizing G, D, D′, A and TPA bands. The appropriateness of these deconvolutions was confirmed via recovery of the correct dispersive behaviours of these bands. It is proposed that the ID/IG ratio is composed of two parts: one associated with the extent of graphitic crystallites (the Tuinstra–Koenig relationship), and a second related to the inter-defect distance. This model was used to successfully determine the variation of the in-plane size and intra-plane defect density along the annealing pathway. It is proposed that the NPC skeleton evolves along the annealing pathway in two stages: below 1600 °C it was dominated by a reduction of in-plane defects with a minor crystallite growth, and above this temperature growth of the crystallites accelerates as the in-plane defect density approaches zero. A significant amount of transpolyacetylene (TPA)-like structures was found to be remaining even at 2400 °C. These may be responsible for resistance to further graphitization of the PFA-based carbon at higher temperatures.

Formation of brominated pollutants during the pyrolysis and combustion of tetrabromobisphenol A at different temperatures

Tetrabromobisphenol A (TBBPA) is the most widely used brominated flame retardant worldwide. A detailed examination of the degradation products emitted during thermal decomposition of TBBPA is presented in the study. Runs were performed in a laboratory furnace at different temperatures (650 and 800 °C) and in different atmospheres (nitrogen and air). More than one hundred semivolatile compounds have been identified by GC/MS, with special interest in brominated ones. Presence of HBr and brominated light hydrocarbons increased with temperature and in the presence of oxygen. Maximum formation of PAHs is observed at pyrolytic condition at the higher temperature. High levels of 2,4-, 2,6- and 2,4,6- bromophenols were found. The levels of polybrominated dibenzo-p-dioxins and furans have been detected in the ppm range. The most abundant isomers are 2,4,6,8-TeBDF in pyrolysis and 1,2,3,7,8-PeBDF in combustion. These results should be considered in the assessment of thermal treatment of materials containing brominated flame retardants.