Alumina-, niobia-, and niobia/alumina-supported NiMoS catalysts: Surface properties and activities in the hydrodesulfurization of thiophene and hydrodenitrogenation of 2,6-dimethylaniline

The activity of NiMoS catalysts supported on niobia, alumina, and niobia/alumina was compared for the thiophene hydrodesulfurization (HDS) and 2,6-dimethylaniline (2,6-DMA) hydrodenitrogenation (HDN) reactions. To evaluate the acidity of the supports and identify the nature of the sulfide sites, adsorption of 2,6-dimethylpyridine, pyridine, and CO was performed and followed by IR spectroscopy. This study has shown that with niobia as a support, the activity of NiMoS catalysts in thiophene HDS and in HDN of 2,6-DMA was no longer promoted by the synergy between Ni and Mo. The absence of synergy between molybdenum and nickel on niobia can be explained by the strong interaction of each metal with niobia at the expense of interaction with each other. Moreover, it has been shown that on a niobia/alumina support, the formation of the NiMoS phase can be directly linked to the presence of alumina not covered by niobia. However, niobia is an interesting support for the HDN of 2,6-DMA, because it favors the formation of xylene through direct ammonia elimination involving low H₂ consumption. The activity for xylene formation on niobia is linked to the electron-deficient nature of the Mo sulfide site, as demonstrated by CO adsorption followed by IR.     

Atmospheric emission of reactive nitrogen during biofuel ethanol production

This paper evaluates emissions to the atmosphere of biologically available nitrogen compounds in a region characterized by intensive sugar cane biofuel ethanol production. Large emissions of NH3 and NOx, as well as particulate nitrate and ammonium, occur at the harvest when the crop is burned, with the amount of nitrogen released equivalent to approximately 35% of annual fertilizer-N application. Nitrogen oxides concentrations show a positive association with fire frequency, indicating that biomass burning is a major emission source, with mean concentrations of NOx doubling in the dry season relative to the wetseason. During the dry season biomass burning is a source of NH3, with other sources (wastes, soil, biogenic) predominant during the wet season. Estimated NO2-N, NH3-N, NO3- -N and NH4+ -N emission fluxes from sugar cane burning in a planted area of ca. 2.2 x 10(6) ha are 11.0, 1.1, 0.2, and 1.2 Gg N yr(-1), respectively.     

Polyvinyl alcohol associated with carbon nanotube scaffolds for osteogenic differentiation of rat bone mesenchymal stem cells

Polyvinyl alcohol (PVAl) hydrogel, alone and reinforced with two types of carbon nanoparticles, was studied in cultured cells to assess its potential use in treating osteochondral defects. The carbon nanoparticles were produced by hot-filament chemical vapour deposition. The carbon material was characterised with a Renishaw Invia Raman microscope system and the morphological particles were characterised with field emission scanning electron microscopy and high-resolution transmission electron microscopy. Cytotoxicity was evaluated by measuring the Vero fibroblast-type cells’ metabolic activity and studying their morphology. The osteogenic differentiation of mesenchymal stem cells obtained from rat bone marrow was evaluated by alkaline phosphatase (ALP) and alizarin red S (ARS) staining. Cell viability and morphology were assessed with thiazolyl blue tetrazolium bromide and scanning electron microscopy, respectively. The materials did not interfere with the viability, metabolic activity, morphology and spreading of either of the cell types analysed. Nodules of mineralised organic matrix were identified with ARS and ALP, confirming osteogenic differentiation. These results indicated higher concentration of ALP and mineralised matrix for PVAl with carbon nanoparticles. The results of this study indicate the potential use of carbon nanoparticles with PVAl hydrogels as orthopaedic biomaterials to treat osteochondral defects, but further in vivo investigations are still necessary.     

A hybrid model for a multiproduct pipeline planning and scheduling problem

Brazilian petrobras is one of the world largest oil companies. Recurrently, it faces a very difficult planning and scheduling problem: how to operate a large pipeline network in order to adequately transport oil derivatives and biofuels from refineries to local markets. In spite of being more economical and environmentally safer, the use of a complex pipeline network poses serious operational difficulties related to resource allocation and temporal constraints. The current approaches known from the literature only consider a few types of constraints and restricted topologies, hence they are far from being applicable to real instances from petrobras. We propose a hybrid framework based on a two-phase problem decomposition strategy. A novel Constraint Programming (CP) model plays a key role in modelling operational constraints that are usually overlooked in literature, but that are essential in order to guarantee viable solutions. The full strategy was implemented and produced very adequate results when tested over large real instances.     

Methods for automatic and assisted image annotation

Personal memories composed of digital pictures are very popular at the moment. To retrieve these media items annotation is required. During the last years, several approaches have been proposed in order to overcome the image annotation problem. This paper presents our proposals to address this problem. Automatic and semi-automatic learning methods for semantic concepts are presented. The automatic method is based on semantic concepts estimated using visual content, context metadata and audio information. The semi-automatic method is based on results provided by a computer game. The paper describes our proposals and presents their evaluations.     

Classes of Timed Automata and the Undecidability of Universality

Universality for deterministic Timed Automata (TA) is PSPACE-complete but becomes highly undecidable when unrestricted nondeterminism is allowed. More precisely, universality for nondeterministic TA is Π₁¹-hard and it is still open whether it is π₁¹-complete. It is interesting to note that the entire arithmetical hierarchy is contained in this computability gap between determinism and nondeterminism. In this paper we consider three types of syntactical restrictions to nondeterministic TA, which may contribute to a better understanding of the universality problem for TA. For the first two types, which are of independent interest, the universality problem is shown to be Π₁¹-complete. For the third one, universality is Π₁⁰-complete, which is the same as saying that the complementary problem is complete in the recursively enumerable class. We also show that all the restrictions define proper subclasses of the class of timed languages defined by nondeterministic TA; and establish the relationships between the classes.     

Applying the redox process to arsenical concentrates

Extensive batch and continuous testing has been completed using a high-temperature, nitric acid pressure leach (Redox) process for oxidizing the refractory gold-containing arsenopyrite tailings presently stockpiled at Snow Lake, Manitoba. This process has achieved up to 99% oxidation of the arsenopyrite compound and precipitated more than 90% arsenic into a stable iron-arsenic compound (resembling ferric arsenate) in less than eight minutes of overall retention time at temperatures of 195–210°C and an oxygen overpressure of 345 kPa. The oxidation step then exposes the contained gold, allowing a recovery of 91.5% in a standard carbon-in-leach circuit. The main advantages of this process are fast reaction rates, the high proportion of arsenic precipitated, and the stability of the precipitate.     

Comparative analysis of available life cycle inventories of cement in the EU

Life cycle inventories (LCIs) are a prerequisite of life-cycle assessments (LCA). This paper conducts a comparative analysis of inventories of several different types of cement produced in Europe. It considers the production of 1 kg of cement from cradle to gate, and all results are based on this mass unit. The reliability of cement inventories is affected by inaccurate or nonrepresentative data, and comparative analysis is difficult due to varying system boundary definitions. Only the four main emissions (CO₂, NOx, SO₂ and dust) are considered. The theoretical model used gives reasonable estimates of emission levels and, thus, can serve as a reference to measured values. In the case of CO₂, this is definitely a feasible alternative to in situ measurements. The emissions derive primarily from the production of clinker, both from the chemical reactions occurring in the kiln and by its fossil fuel consumption.