NANOPARTICLES OF TUNGSTEN AS LOW-COST MONOMETALLIC CATALYST FOR SELECTIVE HYDROGENATION OF 3-HEXYNE

Low-cost tungsten monometallic catalysts containing variable amounts of metal (4.5, 7.1 and 8.5%W) were prepared by impregnating alumina with ammonium metatungstate as an inexpensive precursor. The catalysts were characterized using ICP, XPS, XRD, TPR and hydrogen chemisorption. These techniques revealed mainly WO3-Al2O3 (W6+) species on the surface. The effects of the content of W nanoparticles and reaction temperature on activity and selectivity for the partial hydrogenation of 3-hexyne, a non-terminal alkyne, were assessed under moderate conditions of temperature and pressure. The monometallic catalysts prepared were found to be active and stereoselective for the production of (Z )-3-hexene, had the following order: 7.1WN/A > 8.5 WN/A ≥ 4.5 WN/A. Additionally, the performance of the synthesized xWN/A catalysts exhibited high sensitivity to temperature variation. In all cases, the maximum 3-hexyne total conversion and selectivity was achieved at 323 K. The performance of the catalysts was considered to be a consequence of two phenomena: a) the electronic effects, related to the high charge of W (+6), causing an intensive dipole moment in the hydrogen molecule (van der Waals forces) and leading to heterolytic bond rupture; the H+ and H- species generated approach a 3-hexyne adsorbate molecule and cause heterolytic rupture of the C≡C bond into C- = C+; and b) steric effects related to the high concentration of WO3 on 8.5WN/A that block the Al2O3 support. Catalyst deactivation was detected, starting at about 50 min of reaction time. Electrodeficient W6+ species are responsible for the formation of green oil at the surface level, blocking pores and active sites of the catalyst, particularly at low reaction temperatures (293 and 303 K). The resulting best catalyst, 7.1WN/A, has low fabrication cost and high selectivity for (Z )-3-hexene (94%) at 323 K. This selectivity is comparable to that of the classical and more expensive industrial Lindlar catalyst (5 wt% Pd). The alumina supported tungsten catalysts are low-cost potential replacements for the Lindlar industrial catalyst. These catalysts could also be used for preparing bimetallic W-Pd catalysts for selective hydrogenation of terminal and non-terminal alkynes.

Swine effluent treatment using anaerobic digestion at different loading rates

The industrial swine production is characterized by generation of significant effluent amounts that require treatment. The most adopted practices by Brazilian swine farmers have been wastewater storage in lagoons and its subsequent use as a biofertilizer. Nutrient accumulation in soil and water creates the need for an effective management of these residues. The anaerobic digestion process is an important alternative and low-cost treatment for organic matter reduction. However, its efficiency is limited by the digester capacity of solid degradation, especially at low hydraulic retention times. Thus, the present study aimed to verify the behavior of an upflow anaerobic digester by increasing the organic loading rate. This was accomplished in three stages using, as a parameter, volatile solids at 0.5; 1.0 and 1.5 kgVS m-3 d-1, respectively. This digester model proved to be quite robust and effective in swine manure treatment, achieving high efficiency of volatile solid removal at all stages of the study (stage 1: 61.38%; stage 2: 55.18%; and stage 3: 43.18%). Biogas production was directly related to the increasing organic load, reaching 0.14, 0.85, and 0.86 Nm³ kgVS-1add., respectively, with no significant difference (p<0.05) of biogas methane concentration among the studied stages (73.7, 75.0, and 77.9%).

Mechanical damage during harvest and loading affect orange postharvest quality

Brazil is the world’s largest orange producer; however, part of this production is lost during postharvest. This loss can be minimized by controlling incidence of physical damage throughout the harvest and loading operations. Impacts can negatively modify quantitative and qualitative fruits aspects. The main goal of this study was to measure the impact magnitude in two types of harvest (manual and detachment) and during all steps from picking into bags until loading for transport to the processing industry and additionally evaluating, in laboratory, the physico-chemical quality of the fruit subjected to various impacts, similar to those found in the field. In order to evaluate the impact magnitude, an instrumented sphere was used (760 mm, Techmark, Inc, USA). The following physico-chemical parameters were evaluated during 6-days of storage: weight loss, soluble solids contents, titratable acidity, ascorbic acid content, pH, firmness and peel color. The greatest impacts were observed during harvest, during the detachment practice, and when loading and unloading from bulk storage, with average acceleration values between 249.5 and 531.52G. The impact incidence in oranges were responsible for reducing the soluble solids, titratable acidity, ascorbic acid and weight by to 5.5%; 8.7%; 4.6% and 0.5%, respectively, compared to the control. Impacts during harvest and the various pre-industry manipulation steps must be controlled as they interfere in postharvest quality and physiology of ‘Valência’ oranges.

Modelling of mechanical properties of CRFC composites under flexure loading

Carbon Fibre Reinforced Carbon (CFRC) Composites are increasing their applications due to their high strength and Young’s Modulus at high temperatures in inert atmosphere. Although much work has been done on processing and structure and properties relationship, few studies have addressed the modelling of mechanical properties. This work is divided in two parts. In the first part, a modelling of mechanical properties was carried out for two bi-directional composites using a model based on the Bernoulli-Euler theory for symmetric laminated beams. In the second part, acoustic emission (AE) was used as an auxiliary technique for monitoring the failure process of the composites. Differences in fracture behaviour are reflected in patterns of AE.

Instability of a square sheet under symmetric biaxial loading

An early experiment found that a square rubber sheet under symmetric biaxial loading may not remain square. This curious result has been one of the most instructive examples in finite elasticity. Here thermodynamic considerations are used to analyze this instability.