RESUMO

Biofuels are expected to play a major role in reducing carbon emissions in the aviation sector globally. Farnesane ("2,6,10-trimethyldodecane") is a biofuel derived from the synthesized iso-paraffin route wich can be blended with jet fuel; however, the microbial behavior in farnesane/jet fuel blends remains unknown. The chemical and biological stability of blends should be investigated to ensure they meet the quality requirements for aviation fuels. This work aimed at evaluating the behavior of two fungi Hormoconis resinae (F089) and Exophiala phaeomuriformis (UFRGS Q4.2) in jet fuel, farnesane, and in 10% farnesane blend during simulated storage. Microcosms (150-mL flasks) were assembled with and without fungi containing Bushnell & Haas mineral medium for 28 days at a temperature of 20±2°C. The fungal growth (biomass), pH, surface tension, and changes in the fuel's hydrocarbon chains were evaluated. This study revealed thatthe treatment containing H. resinae showed a biomass of 19 mg, 12 mg, and 2 mg for jet fuel, blend, and farnesane respectively. The pH was reduced from 7.2 to 4.3 observed in jet fuel treatment The degradation results showed that compounds with carbon chains between C9 and C11, in jet fuel, and blend treatments were preferably degraded. The highest biomass (70.9 mg) produced by E. phaeomuriformis was in 10% farnesane blend, after 21 days. However, no significant decrease was observed on pH and surface tension measurements across the treatments as well as on the hydrocarbons when compared to the controls. This study revealed that farnesane neither inhibited nor promoted greater growth on both microorganisms.

Assuntos

RESUMO

Nanozeolites with different crystallographic structures (Nano/TS1, Nano/GIS, Nano/LTA, Nano/BEA, Nano/X, and Nano-X/Ni), functionalized with (3-aminopropyl)trimethoxysilane (APTMS) and crosslinked with glutaraldehyde (GA), were studied as solid supports for Thermomyces lanuginosus lipase (TLL) immobilization. Physicochemical characterizations of the surface-functionalized nanozeolites and nanozeolite-enzyme complexes were performed using XRD, SEM, AFM, ATR-FTIR, and zeta potential measurements. The experimental enzymatic activity results indicated that the nanozeolitic supports functionalized with APTMS and GA immobilized larger amounts of enzymes and provided higher enzymatic activities, compared to unfunctionalized supports. Correlations were observed among the nanozeolite surface charges, the enzyme immobilization efficiencies, and the biocatalyst activities. The catalytic performance and reusability of these enzyme-nanozeolite complexes were evaluated in the ethanolysis transesterification of microalgae oil to fatty acid ethyl esters (FAEEs). TLL immobilized on the nanozeolite supports functionalized with APTMS and GA provided the most efficient biocatalysis, with FAEEs yields above 93% and stability during five reaction cycles. Lower FAEEs yields and poorer catalytic stability were found for nanozeolite-enzyme complexes prepared only by physical adsorption. The findings indicated the viability of designing highly efficient biocatalysts for biofuel production by means of chemical modulation of nanozeolite surfaces. The high biocatalyst catalytic efficiency observed in ethanolysis reactions using a lipid feedstock that does not compete with food production is an advantage that should encourage the industrial application of these biocatalysts.

Assuntos

RESUMO

RATIONALE: Brazil is the largest producer of sugar cane bioethanol in the world. Isotope ratio mass spectrometry (IRMS) is the technique of choice to certify the origin/raw materials for ethanol production, but the lack of certified reference materials (CRMs) for accurate measurements of δ(13) C values traceable to Vienna Pee Dee Belemnite (VPDB), the international zero point for (13) C/(12) C measurements, certified and compatible with gas chromatography (GC)/IRMS instruments may compromise the accuracy of δ(13) C determinations. METHODS: We evaluated the influence of methods for the calibration and normalization of raw δ(13) C values of ethanol samples. Samples were analyzed by GC/C/IRMS using two different GC columns. Different substances were used as isotopic standards for the working gas calibration. The δ(13) C values obtained with the three methods of normalization were statistically compared with those obtained with elemental analyzer (EA)/IRMS, since the δ(13) C results obtained using EA are traceable to VPDB via the NBS 22 reference material. RESULTS: It was observed that both the isotopic reference material for CO2 calibration and the GC column have a major effect on the δ(13) C measurements, leading to a bias of almost 2-3 ‰ in the δ(13) C values. All three methods of normalization were equivalent in performance, enabling an improvement in the GC/C/IRMS accuracy, compared with the EA/IRMS reference values for the samples. CONCLUSIONS: All the methods of CO2 calibration, chromatography and normalization presented in this work demonstrated several sources of traceability and accuracy loss for the determination of δ(13) C values in ethanol fuel samples by GC/C/IRMS. This work has also shown the importance of using proper CRMs traceable to VPBD that should be compatible and certified using GC/C/IRMS, ideally in a wide range of δ(13) C values. This is important not only for bioethanol fuel samples, but also for many analytes commonly analyzed by IRMS.

RESUMO

The process of biodiesel production by the hydroesterification route that is proposed here involves a first step consisting of triacylglyceride hydrolysis catalyzed by lipase from Thermomyces lanuginosus (TL 100L) to generate free fatty acids (FFAs). This step is followed by esterification of the FFAs with alcohol, catalyzed by niobic acid in pellets or without a catalyst. The best result for the enzyme-catalyzed hydrolysis was obtained under reaction conditions of 50% (v/v) soybean oil and 2.3% (v/v) lipase (25 U/mL of reaction medium) in distilled water and at 60°C; an 89% conversion rate to FFAs was obtained after 48 hours of reaction. For the esterification reaction, the best result was with an FFA/methanol molar ratio of 1:3, niobic acid catalyst at a concentration of 20% (w/w FFA), and 200°C, which yielded 92% conversion of FFAs to soy methyl esters after 1 hour of reaction. This study is exceptional because both the hydrolysis and the esterification use a simple reaction medium with high substrate concentrations.