Extração enzimática de óleo e produção in situ de biodiesel a partir da Moringa oleífera Lam

With the growth and development of modern society, arises the need to search for new raw materials and new technologies which present the "clean" characteristic, and do not harm the environment, but can join the energy needs of industry and transportation. The Moringa oleifera Lam, plant originating from India, and currently present in the Brazilian Northeast, presents itself as a multi-purpose plant, can be used as a coagulant in water treatment, as a natural remedy and as a feedstock for biodiesel production. In this work, Moringa has been used as a raw material for studies on the extraction and subsequently in the synthesis of biodiesel. Studies have been conducted on various techniques of Moringa oil extraction (solvents, mechanical pressing and enzymatic), being specially developed an experimental design for the aqueous extraction with the aid of the enzyme Neutrase© 0.8 L, with the aim of analyzing the influence variable pH (5.5-7.5), temperature (45-55°C), time (16-24 hours) and amount of catalyst (2-5%) on the extraction yield. In relation to study of the synthesis of biodiesel was initially carried out a conventional transesterification (50°C, KOH as a catalyst, methanol and 60 minutes reaction). Next, a study was conducted using the technique of in situ transesterification by using an experimental design variables as temperature (30-60°C), catalyst amount (2-5%), and molar ratio oil / ethanol (1:420-1:600). The extraction technique that achieved the highest extraction yield (35%) was the one that used hexane as a solvent. The extraction using 32% ethanol obtained by mechanical pressing and extraction reached 25% yield. For the enzymatic extraction, the experimental design indicated that the extraction yield was most affected by the effect of the combination of temperature and time. The maximum yield obtained in this extraction was 16%. After the step of obtaining the oil was accomplished the synthesis of biodiesel by the conventional method and the in situ technique. The method of conventional transesterification was obtained a content of 100% and esters by in situ technique was also obtained in 100% in the experimental point 7, with a molar ratio oil / alcohol 1:420, Temperature 60°C in 5% weight KOH with the reaction time of 1.5 h. By the experimental design, it was found that the variable that most influenced the ester content was late the percentage of catalyst. By physico-chemical analysis it was observed that the biodiesel produced by the in situ method fell within the rules of the ANP, therefore this technique feasible, because does not require the preliminary stage of oil extraction and achieves high levels of esters

Modelagem e simulação da solubilização da parafina em tubos circulares e em regime laminar

O óleo produzido nos novos campos de petróleo está cada vez mais parafínico e viscoso, com isso, à medida que o óleo é escoado, parafinas são depositadas sobre as paredes internas do tubo, e ao longo do tempo, tendem a reduzir drasticamente a área transversal ao escoamento. Visando estudar o processo de solubilização da parafina em dutos, esse trabalho objetiva desenvolver modelos matemáticos que represente o processo, com base nos fenômenos envolvidos no mesmo tais como transferência de massa, transferência de energia e equilíbrio sólido-líquido, implementando-os em um ambiente de desenvolvimento VBA (Visual Basic) for Excel ®. O presente trabalho foi realizado em quatro etapas: i) modelagem dos fenômenos de transferência de calor e massa, ii) modelagem da rotina dos coeficientes de atividade através do modelo UNIFAC e modelagem do sistema de equilíbrio sólido-líquido; iii) modelagem matemática do processo de solubilização e cálculo da espessura da parafina ao longo do tempo; iv) implementação dos modelos em um ambiente de desenvolvimento VBA for Excel® e criação de um simulador com uma interface gráfica, para simular o processo de solubilização da parafina depositada em dutos e sua otimização. O simulador conseguiu produzir soluções bastante adequadas, mantendo continuidade das equações diferenciáveis do balanço de energia e de massa, com uma interpretação física viável, sem a presença de dissipação de oscilações nos perfis de temperatura e massa. Além disso, esse simulador visa permitir a simulação nas diversas condições de escoamento, bem como compreender a importância das variáveis (vazão, temperatura de entrada, temperatura externa, cadeia carbônica do solvente). Através dos resultados foram possíveis verificar os perfis de temperatura, fração molar e o de solubilização

Avaliação cinética e potencial do Nb2O5 obtido a partir de um complexo de nióbio para formação do oleato de metila através da reação de esterificação do ácido oleico

Among the heterogeneous catalysts materials made from niobium show up as an alternative to meet the demand of catalysts for biodiesel production. This study aims to evaluate the potential of a heterogeneous catalyst derived from a complex of niobium in the reaction of methyl esterification of oleic acid. The catalyst was synthesized after calcination at different temperatures of a niobium complex ((NH4)3[NbO(C2O4)3].H2O) generating a niobium oxide nanostructure with a different commercial niobium oxide used to synthesize the complex. The commercial niobium oxide, the complex niobium and niobium catalyst were characterized by thermogravimetry (TG and DTA), surface area analysis (BET), scanning electron microscopy (SEM) and X-ray diffraction (XRD), showing the catalyst has researched morphological and crystallographic indicating a catalytic potential higher than that of commercial niobium oxide characteristics. Factorial with central composite design point, with three factors (calcination temperature, molar ratio of alcohol/oleic acid and mass percentage of catalyst) was performed. Noting that the optimal experimental point was given by the complex calcination temperature of 600°C, a molar ratio alcohol/oleic acid of 3.007/1 and the catalyst mass percentage of 7.998%, with a conversion of 22.44% oleic acid in methyl oleate to 60 min of reaction. We performed a composite linear and quadratic regression to determine an optimal statistical point of the reaction, the temperature of calcination of the complex at 450°C, the molar ratio of alcohol/oleic acid 3.3408/1 and mass percentage of catalyst of 7.6833% . Kinetic modeling to estimate parameters for heterogeneous catalysis it set well the experimental results with a final conversion of 85.01% with 42.38% of catalyst and without catalyst at 240 min reaction was performed. Allowing to evaluate the catalyst catalytic studied has the potential to be used in biodiesel production

Equilíbrio líquido-líquido para o sistema biodiesel de óleo de semente de melão (Cucumis melo l.) + metanol + glicerina

Rio Grande do Norte, northeast state from Brazil, it is the greatest producer and exporter of yellow melon, well known as Spanish melon. Despite the consumption of this fruit to be mainly its pulp, melon seeds are an important source of lipids considered an industrial residue it has been discharge product. The use of oilseeds in order to produce biodiesel establishes an important raw material and the increase of its production promotes the national development of the agriculture. In this background, the aim of this work has been to use oil from seeds of yellow melon to produce biodiesel and to accomplish a study of the phase equilibrium of the system evolving biodiesel, methanol and glycerin. The biodiesel was obtained by oil transesterification through methylic route with molar ratio 1:9.7 (oil:alcohol) and with a mass of NaOH of 0.5% from the oil mass; the reaction time was 73 minutes at 55 °C. A yield of 84.94% in biodiesel was achieved. The equilibria data present a well-characterized behavior with a great region of two phases. The tie lines indicate that methanol has a best solubility in the phase that is rich in glycerin. Consistency of the experimental data was made based on Othmer-Tobias and Hand correlations which values above 0.99 were found to correlation coefficients, this fact confers a good thermodynamic consistency to the experimental data. NRTL and UNIQUAC models were employed to predict liquid-liquid equilibrium of this system. It was observed a better concordance of the results when NRTL was applied (standard deviation 1.25%) although the UNIQUAC model has presented a quite satisfactory result either (standard deviation 2.70%). The NRTL and UNIQUAC models were also used to evaluate the effect of temperature in the range of 328 K to 358 K, in which a little change in solubility with respect to the data obtained at 298 K was observed, thus being considered negligible the effect of temperature

Síntese de Fischer-Tropsch sobre perovskitas LayCu0,4Fe0,6O3

The current natural gas production of 52 Mm3d-1 and the large projects for its expansion has been setting new boundaries for the Brazilian industry of oil and gas. So far, one of the biggest challenges regards to the logistics for gas transportation from offshore fields. Therefore, the transformation of natural gas into gasoline, diesel and/or olefins via Fischer-Tropsch synthesis would be an alternative to this matter. In this work, the production of hydrocarbons by Fischer-Tropsch synthesis in a slurry reactor was investigated and a perovskite-type catalyst (LayCu0,4Fe0,6O3 ± d) was used with y varying from 0 to 1 on a molar basis. In addition, Nb2O5 support was also applied in order to observe the selectivity of the produced hydrocarbons by the Fischer-Tropsch process. It is shown that the hydrogen conversion was influenced by the support as well as the different phases of the samples. The kinetic results for the CO2 production suffered great influence with the introduction of the Nb2O5 support throughout the series of samples studied. The catalysts allowed obtaining welldefined cuts of hydrocarbons in the range of C1-C6 and C17-C28, and these results were clearly influenced by the support and the lanthanum content. The higher olefin/paraffin ratio obtained was 1.8 when using a non-supported perovskite with y equal to 0.8. This would indicate the suitability of using this material for the production of olefins

Concepção e estudo de um biofiltro para tratamento de compostos orgânicos voláteis COVs

In the last decade, biological purification of gaseous waste has become an important alternative to many conventional methods of exhaust air treatment. More recently, biofiltration has proved to be an effective and inexpensive method for the treatment of air contaminated with volatile organic compounds (VOCs). A biofilter consists in a reactor packed with a porous solid bed material, where the microorganisms are fixed. During the biofiltration process, polluted air is transported through the biofilter medium where the contaminant is degraded. Within the biofilm, the pollutants in the waste gases are energy and carbon sources for microbial metabolism and are transformed into CO2, water and biomass. The bed material should be characterized by satisfactory mechanical and physical properties as structure, void fraction, specific area and flow resistance. The aim of this research was the biofilter construction and study of the biological degradation of ethanol and toluene, as well as the modeling of the process. Luffa cylindrica is a brazilian fiber that was used as the filtering material of the present work. The parameters and conditions studied were: composition of nutrients solution; effect of microflorae strains, namely Pseudomanas putida and Rhodococcus rhodochrous; waste gas composition; air flow rate; and inlet load of VOCs. The biofilter operated in diffusion regime and the best results for remotion capacity were obtained when a microorganisms consortion of Pseudomanas putida and Rhodococcus rhodochrous,were used, with a gas flow rate of 1 m3.h-1 and molar ratio nitrogene/phosphore N/P=2 in the nutrients solution. The maximum remotion capacity for ethanol was around 90 g.m-3.h-1 and 50 g.m-3.h-1 to toluene. It was proved that toluene has inhibitory effect on the ethanol remotion When the two VOCs were present in the same waste gas, there was a decrease of 40% in ethanol remotion capacity. Luffa cylindrica does not present considerable pressure drop. Ottengraf and van Lith models were used to represent the results obtained for ethanol and toluene, respectively. The application of the transient model indicated a satisfactory approximation between the experimental results obtained for ethanol and toluene vapors biofiltration and the ones predicted it

Recuperação de fósforo por cristalização de estruvita

This study investigated the influence of the molar ratio, the phosphorus initial concentration, the mixture gradient, mixing time, pH and the secondary nucleation on struvite s crystallization in synthetic water in batch reactors. The study was divided into two stages. The first investigated struvite s crystallization at different Mg:N:P molar ratios and at different initial concentrations of magnesium, nitrogen and phosphorus. It was also evaluated the importance of secondary nucleation on the struvite s crystallization. In the second, five parameters were tested to evaluate their influence on the struvite s crystallization, which were: Mg:N:P molar ratio, initial concentration of phosphate, mixing time, mixture gradient and pH. The best conditions for struvite s crystallization were: Mg:N:P = 1,3:1:1 molar ratio; mixture gradient = 60 rpm, pH = 10.0, mixing time = 5 minutes and high initial concentrations of the constituent ions of struvite. Furthermore, the use of struvite crystals as seed influenced positively on the struvite s crystallization

Effects of oxidation of lysozyme by hypohalous acids and haloamines on enzymatic activity and aggregation

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Antitumor and antimycobacterial activities of cyclopalladated complexes: X-ray structure of [Pd(C-2,N-dmba)(Br)(tu)] (dmba = N,N-dimethylbenzylamine, tu = thiourea)

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

6-Mercaptopurine complexes with silver and gold ions: Anti-tuberculosis and anti-cancer activities

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

On the incorporation of the non-steroidal anti-inflammatory naproxen into cationic O/W microemulsions

Microemulsions (ME) containing hexadecyltrimethylammonium bromide (HTAB)/ethanol as surfactant, isopropylmyristate (IM) or butylstearate (BS) as oil phase and aqueous buffer were studied. Pseudo-ternary phase diagrams of the investigated systems were obtained at constant surfactant/cosurfactant molar ratio (1:5) by titration in order to characterize the proportions between the components to obtain clear systems. Oil in water microemulsions were prepared in a wide range of phase volume (phi). UV-vis absorption spectra of naproxen at pH 5.5 showed that the solubility of Np increases significantly in the presence of O/W ME in high phase volumes. For both, IM and BS microemulsions, the dynamic light scattering experiments showed that the size of the oil droplets remains constant in low values of phi, increasing abruptly in high phi values. Phase solubility study revealed that for both IM and BS microemulsions, the drug incorporation followed a straight-line profile in all range of phi. The data could be analyzed through the phase-separation model and the association constants (K) calculated varied from 27 to 90 M-1, depending on the pH and on the microemulsion oil phase. (c) 2005 Elsevier B.V. All rights reserved.

Synthesis, X-ray structure and antimycobacterial activity of silver complexes with alpha-hydroxycarboxylic acids

In this paper, synthesis, characterization and antimycobacterial properties of a new water-soluble complex identified as silver-mandelate are described. Elemental and thermal analyses are consistent with the formula [Ag(C6H5C(OH)COO)](n). The polymeric structure was determined by single X-ray diffraction and the two-dimensional structure is based on the bis(carboxylate-O,O') dimer [Ag-O, 2.237(3), 2.222(3) angstrom]. The structure is extended along both the b and c axes through two oxygen atoms of a bidentate alpha-hydroxyl-carboxylate residue [Ag-OH(hydroxyl), 2.477(3) angstrom; Ag-O(carboxylate), 2.502(3) angstrom; O-Ag-O, 63.94(9)degrees]. A strong d(10)-d(10) interaction was observed between two silver atoms. The Ag...Ag distance is 2.8307(15) angstrom. The NMR C-13 spectrum in D2O shows that coordination of the ligand to Ag(l) occurs through the carboxylate group in solution. Potentiometric titration shows that only species with a molar metaHigand ratio of 2:2 are formed in aqueous solution. The mandelate complex and the silver-glycolate, silver-malate and silver-hydrogen-tartarate complexes were tested against three types of mycobacteria, Mycobacterium avium, Mycobacterium tuberculosis and Mycobacterium kansasii, and their minimal inhibitory concentration (MIC) values were determined. The results show that the four complexes are potential candidates for antiseptic or disinfectant drugs for discharged secretions of patients affected with tuberculosis. (c) 2006 Published by Elsevier B.V.

Piroxicam encapsulated in liposomes: Characterization and in vivo evaluation of topical anti-inflammatory effect

Liposomes of soya phosphatidylcholine, cholesterol, and stearylamine (molar ratio 6/3/1) and 0.1% alpha-tocopherol were prepared by the extrusion of multilamellar vesicles through 0.2-mu m polycarbonate membrane. Liposomes were characterized by electron transmission microscopy, and the mean structure diameter was 278 nm. The encapsulation efficiency obtained was 12.73%. The topical anti-inflammatory effect was evaluated in vivo by the cotton pellet granuloma method. We analyzed free piroxicam at 4 mg/kg, piroxicam encapsulated in liposomes added to 1.5% hydroxyethylcellulose (HEC) gel at 1.6 mg/kg, and piroxicam encapsulated in liposomes added to HEC gel at 4 mg/kg; the inhibition of inflammation obtained was 21.1%, 32.8%, and 47.4%, respectively. These results showed that the encapsulation of piroxicam produced an increase of topical anti-inflammatory effect, suggesting that the inhibition of inflammation can be obtained with lower drug concentrations.

Effect of vesicles of dimethyldioctadecylammonium chloride and phospholipids on the rate of decarboxylation of 6-nitrobenzisoxazole-3-carboxylate

Sonicated mixtures of dimethyldioctadecylammonium chloride (DODAC), egg phosphatidylcholine (PC), dimyristoyl phosphatidylcholine (DMPC), and dipalmitoyl phosphatidylcholine (DPPC) were used to analyze vesicle effects on the rate of decarboxylation of 6-nitrobenzisoxazol-3-carboxylic acid (Nboc). Electron microscopic images of the vesicles were obtained with trehalose, a know cryoprotector. Phase diagrams and phase transitions temperatures of the vesicle bilayers were determined. Nboc decarboxylation rates increased in the presence of vesicles prepared with both phospholipids and DODAC/phospholipid mixtures. Quantitative analysis of vesicular effects was done using pseudophase models. Phospholipids catalyzed up to 140-fold while the maximum catalysis by DODAC/lipid vesicles reached 800-fold. Acceleration depends on alkyl chain length, fatty acid insaturation of the lipids, and the DODAC/phospholipid molar ratio. Catalysis is not related to the liquid crystalline-gel state of the bilayer and may be related to the relative position of Nboc with respect to the interface.

Propriedades ópticas de nanocristais de SiGe: efeitos de dopagem e desordem

We have used ab initio calculations to investigate the electronic structure of SiGe based nanocrystals (NC s). This work is divided in three parts. In the first one, we focus the excitonic properties of Si(core)/Ge(shell) and Ge(core)/Si(shell) nanocrystals. We also estimate the changes induced by the effect of strain the electronic structure. We show that Ge/Si (Si/Ge) NC s exhibits type II confinement in the conduction (valence) band. The estimated potential barriers for electrons and holes are 0.16 eV (0.34 eV) and 0.64 eV (0.62 eV) for Si/Ge (Ge/Si) NC s. In contradiction to the expected long recombination lifetimes in type II systems, we found that the recombination lifetime of Ge/Si NC s (τR = 13.39μs) is more than one order of magnitude faster than in Si/Ge NC s (τR = 191.84μs). In the second part, we investigate alloyed Si1−xGex NC s in which Ge atoms are randomly positioned. We show that the optical gaps and electron-hole binding energies decrease linearly with x, while the exciton exchange energy increases with x due to the increase of the spatial extent of the electron and hole wave functions. This also increases the electron-hole wave functions overlap, leading to recombination lifetimes that are very sensitive to the Ge content. Finally, we investigate the radiative transitions in Pand B-doped Si nanocrystals. Our NC sizes range between 1.4 and 1.8 nm of diameters. Using a three-levels model, we show that the radiative lifetimes and oscillator strengths of the transitions between the conduction and the impurity bands, as well as the transitions between the impurity and the valence bands are strongly affected by the impurity position. On the other hand, the direct conduction-to-valence band decay is practically unchanged due to the presence of the impurity