This work provides a general insight on lipase-catalyzed synthesis of geranyl acetate through esterification of geraniol with acetic acid. Although this reaction is relatively well known, the replacement of organic solvents by supercritical fluids is fairly recent and the role of CO2 is still not completely understood. Therefore, reactions were performed with Lipozyme® RM IM and Novozym® 435 as biocatalysts, and hexane and CO2 as solvents. For similar reaction conditions, geraniol conversions obtained using hexane were much higher, rather than supercritical CO2 (scCO2, 82.9% versus 12.0% after 4 h). The results obtained indicated that CO2 might help the migration of water from the enzyme surface to reaction bulk and then to the vapor phase. Thus, by increasing the vapor phase extension, the geraniol conversion enhanced to 60.5% after 4 h. Such improvement represents one step forward to comprehend the influence of CO2, a safer and greener solvent as compared to hexane.

In this work, two catalytic systems combining Lewis and Brønsted acids (ZnCl2/HCl and AlCl3/HCl) were applied in a tetrahydrofuran (THF)/NaClaq biphasic system to produce furan compounds from plant polysaccharides. The following cellulosic matrices were applied for this purpose: α-cellulose, microcrystalline cellulose and both native and steam-exploded sugarcane bagasse. The AlCl3/HCl catalytic system afforded the best yields for α-cellulose conversion to furan compounds (hydrolysis followed by dehydration). The highest yields of 5-(hydroxymethyl)-furfural (HMF) and furfural were 44.0 and 92.2% for AlCl3/HCl and 36.5 and 81.4% for ZnCl2/HCl, respectively. Cellulosic materials with lower crystallinity indexes afforded the best performance in hydrolysis followed by dehydration, giving relatively high yields of HMF and furfural. The HMF yields were similar for both native and steam-exploded sugarcane bagasse and the presence of lignin had a negative effect on HMF production. The highest furfural yield from native sugarcane bagasse was 60.6% with AlCl3/HCl catalytic system.

The steam explosion was carried out in the absence (autohydrolysis) and presence of phosphoric acid to evaluate the effects of temperature (180 and 210 °C), acid concentration (0 and 19 mg g-1, dry basis) and pretreatment time (5 and 10 min) on the structure and reactivity of sugarcane bagasse. Glucan recovery was used as the main response factor for pretreatment optimization through a central composite design. Autohydrolysis at 210 °C for 10 min had a good pretreatment performance but phosphoric acid catalysis (19 mg g-1) resulted in better yields under considerably milder conditions (180 °C, 5 min). Hydrolysis of both substrates for 96 h using 8 wt.% total solids and 30 mg g-1 Cellic® CTec2 (Novozymes) provided total glucose yields of 75% in average. The production of cellulosic ethanol was assessed by both separate and simultaneous hydrolysis and fermentation using Saccharomyces cerevisiae. Freeze-drying of pretreatment water solubles reduced the concentration of furfural, hydroxymethylfurfural and acetic acid by more than 80% and this eliminated their inhibitory effect on yeast fermentation.

Polímeros sintéticos são largamente utilizados em diversos produtos devido às suas propriedades físicas, químicas e facilidade de transformação. O poli(cloreto de vinila), conhecido como PVC, é um dos polímeros mais versáteis desenvolvidos pelo homem, de grande utilidade para a sociedade moderna. Suas aplicações incluem: janelas, calhas de chuva, revestimentos de paredes, portas, papel de parede, mangueiras, brinquedos, calçados, bolsas de sangue e tubos para condução de água. Em todas estas aplicações são utilizados aditivos junto à resina de PVC, sendo que um dos aditivos mais utilizados é o plastificante. Este estudo apresenta a análise comparativa de formulações flexíveis de PVC, baseada em dois plastificantes de origem renovável (óleo vegetal modificado - OVM e óleo vegetal modificado e epoxidado - OVME), e também dois plastificantes petroquímicos convencionais, di(2-etilhexil) ftalato - (DEHP) ou DOP e di(2-etilhexil) adipato - (DEHA) ou DOA. Não foram observadas diferenças significativas entre as propriedades mecânicas das formulações. Os diferentes plastificantes demonstram influenciar na dureza e resistência química das formulações, sendo que o grupo epóxi e a maior massa molar no plastificante vegetal apresentam maior compatibilidade com a resina de PVC. A análise de MEV apresenta uma provável exudação do plastificante OVM da matriz do PVC.

Synthetic polymers have been widely used in manufactured products because of their physical and chemical properties and low cost of production. Poly(vinyl chloride), called PVC, is a versatile, inexpensive plastic whose use has become pervasive in modern society. Its applications include window frames, rain gutters, wall paneling, doors, wallpapers, flooring, garden furniture, toys, blood bags and pipes. In all of these applications additives are used, with plasticizers being among the most important. This work shows a comparative study among distinct compositions of flexible PVC - based on two vegetable plasticizers from renewable sources (modified vegetable oil - OVM and epoxidized modified vegetable oil - OVME), in addition to two conventional petrochemical plasticizers, called di(2-ethylhexyl) phthalate-(DEHP) and di(2-ethylhexyl) adipate-(DEHA). No significant differences were observed in the mechanical behavior of the compositions evaluated. The plasticizers affected the hardness and chemical resistance to n-heptane for the compositions. The epoxi group and the high molar mass from vegetable plasticizers showed better compatibility with the PVC resin. The analyses by SEM showed a probable exudation of OVM from the PVC matrix.

O efeito de antioxidantes sintéticos, como BHT (butil-hidroxitolueno), BHA (butil-hidroxianisol) e TBHQ (t-butil-hidroxiquinona), foi avaliado sobre o período de indução de uma amostra de ésteres etílicos de óleo de soja de baixa estabilidade à oxidação, empregando o método Rancimat (EN14112). Efeitos de interação também foram investigados empregando-se um planejamento fatorial, que teve como níveis mínimos e máximos as concentrações de zero e 1500 ppm de cada antioxidante. Dentre os antioxidantes sintéticos avaliados, o BHT apresentou maior eficácia nas concentrações compreendidas entre 200 e 7000 ppm. O TBHQ apresentou maior potencial estabilizador quando utilizado em concentrações mais elevadas, enquanto que o BHA mostrou-se pouco efetivo nesta amostra, sendo que em concentrações superiores a 2000 ppm, não proporcionou qualquer acréscimo do período de indução. O uso combinado destes antioxidantes, nos níveis testados neste estudo, não evidenciou qualquer efeito sinérgico positivo que justifique o seu uso em misturas binárias ou ternárias.

The effect of synthetic antioxidants such as BHT (butyl-hydroxytoluene), BHA (butyl-hydroxyanisol) and TBHQ (t-butyl-hydroxyquinone) was evaluated on the induction time of soybean oil ethyl esters with low oxidation stability, employing the Rancimat method (EN14112). Interaction effects were also investigated by employing a 2³ factorial design, which had as minimum and maximum levels the concentrations of zero and 1500 ppm of each antioxidant. Among the synthetic antioxidants evaluated, BHT displayed the highest effectiveness in the concentration range from 200 to 7000 ppm. TBHQ displayed a greater stabilizing potential when used at higher concentrations (8000 ppm), while BHA was found to provide no noticeable increase in the induction time at concentrations greater than 2000 ppm. The combined use of these antioxidants, at the levels tested in this study, yielded no evidence of any positive synergic effect that would justify their use in binary or ternary mixtures.

In this work, the utilization of used frying oil for the production of biodiesel is presented. The performance of biodiesel in diesel engines, as well as the characterization of the emissions derived from this process, are also discussed and compared to the emissions derived from engines running on unused vegetable oils and conventional diesel.