Separação e determinação quantitativa dos alcanos lineares e dos cíclicos/ramificados em petróleos brasileiros por aduto de ureia e cromatografia gasosa: um estudo de caso revisitado

A complete analysis of oils and their fractions allows correlations to be defined between their composition and derivatives or related geological materials. This work focused on optimization and implementation of a method for separation and quantification of n-alkanes in Brazilian oil samples by urea adduction and GC-FID techniques. Ten samples with different ºAPI were analyzed in triplicate to quantify individual n-alkanes and cyclic/branched alkane fraction. For individual quantification of n-alkanes, internal standardization with deuterated n-tetracosane was used. The use of urea adduction for the separation and quantification of n-alkanes was highly effective, with recovery values of above 80%.

ESTERIFICAÇÃO E TRANSESTERIFICAÇÃO SIMULTÂNEAS DE ÓLEOS ÁCIDOS UTILIZANDO CARBOXILATOS LAMELARES DE ZINCO COMO CATALISADORES BIFUNCIONAIS

Palm oil containing 40% fatty acids was converted to methyl esters using zinc carboxylates as the esterification/transesterification catalyst. The reaction was optimized using a factorial design in which the effects of the alcohol:fatty acids molar ratio (MRAG) and the catalyst concentration (CAT) were assessed. The best conversion was achieved with CAT at 4 wt% and MRAG at 4:1. However, the solid catalyst presented significant structural changes after use. For instance, laurate anions were replaced by carboxylates of higher molecular mass, leading to the formation of a new catalytically active layered structure. Also, the glycerin obtained as a co-product contained 86 wt% glycerol.

COMPOSIÇÃO QUÍMICA E TEMPERATURA DE CRISTALIZAÇÃO DE ÉSTERES OBTIDOS DE QUATRO ÓLEOS VEGETAIS EXTRAÍDOS DE SEMENTES DE PLANTAS DO CERRADO

The seed oils from four plants (Scheelea phalerata, Butia capitata, Syagrus romanzoffiana, Terminalia cattapa) found in Mato Grosso do Sul were extracted at good yields. Alkaline transesterification of these seed oils to esters using methanol and ethanol was studied and also produced good yields. Oleic acid (30.5/32.3%), lauric acid (30.7/32.9%) methyl and ethyl esters, were the main components of transesterification of the oils from Scheelea phalerata and Syagrus romanzoffiana. Lauric acid (42.2%), capric acid (15.9%) and caprylic acid (14.6%) methyl and ethyl esters were the main ester components of transesterification of the oil from Butia capitata. Oleic acid (37.8%), palmitic acid (33.5%) and linoleic acid (22.6%) methyl and ethyl esters were the main components of transesterification of oil from Terminalia catappa. Based on differential scanning calorimetry (DSC) studies, the first crystallization peak temperature of esters was observed. Esters derived from oils of the family Arecaceae (Scheelea phalerata, Butia capitata, Syagrus romanzoffiana) showed the lowest points of crystallization, despite having high levels of saturated fat. Esters of Terminalia cattapa oil, rich in unsaturated fat, showed the highest crystallization temperature. This difference in behavior is probably related to the high concentration of esters derived from lauric acid and palmitic acid.

HS-SPME-GC-MS ANALYSIS OF VOLATILE AND SEMI-VOLATILE COMPOUNDS FROM DRIED LEAVES OF Mikania glomerata Sprengel

This paper reports on the identification of volatile and semi-volatile compounds and a comparison of the chromatographic profiles obtained by Headspace Solid-Phase Microextraction/Gas Chromatography with Mass Spectrometry detection (HS-SPME-GC-MS) of dried leaves of Mikania glomerata Sprengel (Asteraceae), also known as 'guaco.' Three different types of commercial SPME fibers were tested: polydimethylsiloxane (PDMS), polydimethylsiloxane/divinylbenzene (PDMS/DVB) and polyacrylate (PA). Fifty-nine compounds were fully identified by HS-SPME-HRGC-MS, including coumarin, a marker for the quality control of guaco-based phytomedicines; most of the other identified compounds were mono- and sesquiterpenes. PA fibers performed better in the analysis of coumarin, while PDMS-DVB proved to be the best choice for a general and non-selective analysis of volatile and semi-volatile guaco-based compounds. The SPME method is faster and requires a smaller sample than conventional hydrodistillation of essential oils, providing a general overview of the volatile and semi-volatile compounds of M. glomerata.

ANÁLISE COMPARATIVA DO CONTEÚDO EM ESTEROIDES LIVRES DE DIFERENTES ÓLEOS, GORDURAS E BIODIESEIS POR CROMATOGRAFIA GASOSA

In this study, the percentage content of free steroid in oils, fats and biodiesel was analyzed. For this, the saponification reaction on a microscale was used, and this procedure for extraction of unsaponifiable fraction was studied in several experimental steps. After the process of saponification, the unsaponifiable fraction was analyzed by gas chromatography with flame ionization detector, where all steroids present in each oil, fat and biodiesel were identified and their contents determined and compared to their respective biodiesel. A reduction in unsaponifiable fraction of each oil and fat and its biodiesel was noted, as well as a reduction in the content of free steroids. The results showed that, compared to the sedimentation problem of steroids in biodiesel, some raw materials, such as chicken fat and babassu oil may be promising because they have low content and high reduction percentages of steroids when converted to biodiesel.

CHEMOSTAT, UM SOFTWARE GRATUITO PARA ANÁLISE EXPLORATÓRIA DE DADOS MULTIVARIADOS

The objective of this work was to develop a free access exploratory data analysis software application for academic use that is easy to install and can be handled without user-level programming due to extensive use of chemometrics and its association with applications that require purchased licenses or routines. The developed software, called Chemostat, employs Hierarchical Cluster Analysis (HCA), Principal Component Analysis (PCA), intervals Principal Component Analysis (iPCA), as well as correction methods, data transformation and outlier detection. The data can be imported from the clipboard, text files, ASCII or FT-IR Perkin-Elmer “.sp” files. It generates a variety of charts and tables that allow the analysis of results that can be exported in several formats. The main features of the software were tested using midinfrared and near-infrared spectra in vegetable oils and digital images obtained from different types of commercial diesel. In order to validate the software results, the same sets of data were analyzed using Matlab© and the results in both applications matched in various combinations. In addition to the desktop version, the reuse of algorithms allowed an online version to be provided that offers a unique experience on the web. Both applications are available in English.

MICROESTRUTURA E PROPRIEDADES DE FILMES DE AMIDO-ÁLCOOL POLIVINÍLICO-ALGINATO ADICIONADOS DE ÓLEOS ESSENCIAIS DE COPAÍBA E CAPIM LIMÃO

AbstractFilms obtained by blends between starch and other polymers and films developed with the addition of an oil can show higher water vapor barriers and improved mechanical properties. Films with starch/PVOH/alginate were obtained by adding copaiba and lemongrass essential oils (EOs). Films without oil served as the control. The microstructure, water vapor permeability (PVA), mechanical properties, and antifungal activity were determined for the films. The effects of the addition of the EOs on the properties of the films were dependent of the concentration and type of oil. The films with 0.5% lemongrass EO were similar to the control films. These films showed a 2.02 × 10-12 g s-1Pa m-1 PVA, 11.43 MPa tensile stress, 13.23% elongation, and 247.95 MPa/mm resistance at perforation. The addition of 1% of copaiba EO increased the PVA from 0.5 × 10-12 to 12.1 × 10-12 g s-1 Pa m-1 and the diffusion coefficient from 0.17 × 10-8 to 7.15 × 10-8m2/day. Films with quantities of EOs displayed fissures and micropores; the control films developed micropores with smaller diameters than films with EOs. The addition of EOs did not change the resulting infrared spectrum of the films. The films with oil displayed a diminished development of the Fusarium sp. culture, and the film without EOs did not display notable differences in the development of the culture. The starch/PVOH/alginate films with 0.5% lemongrass EO were the most suited for the development of a packaging active system.

ANÁLISE EXPLORATÓRIA DAS CONCENTRAÇÕES DOS METAIS NA, CA, MG, SR E FE EM EXTRATO AQUOSO DE PETRÓLEO, DETERMINADOS POR ICP OES, APÓS OTIMIZAÇÃO EMPREGANDO PLANEJAMENTO DE EXPERIMENTOS

AbstractThe purpose of this study was to evaluate the best operating conditions of ICP OES for the determination of Na, Ca, Mg, Sr and Fe in aqueous extract of crude oil obtained after hot extraction with organic solvents (ASTM D 6470-99 modified). Thus, the full factorial design and central composite design were used to optimize the best conditions for the flow of nebulization gas, the flow of auxiliary gas, and radio frequency power. After optimization of variables, a study to obtain correct classification of the 18 samples of aqueous extract of crude oils (E1 to E18) from three production and refining fields was carried out. Exploratory analysis of these extracts was performed by principal component analysis (PCA), hierarchical cluster analysis (HCA) and linear discriminant analysis (LDA), using the original variables as the concentration of the metals Na, Ca, Mg, Sr and Fe determined by ICP OES.

MICROEMULSÕES: COMPONENTES, CARACTERÍSTICAS, POTENCIALIDADES EM QUÍMICA DE ALIMENTOS E OUTRAS APLICAÇÕES

Microemulsions (MEs) are thermodynamically stable systems consisting of nanosized droplets dispersed in a solvent continuous medium (known as pseudo-phase), which is immiscible with the dispersed phase. These systems consist of water, a hydrophobic solvent called "oil," an amphiphile and often, a co-surfactant that is normally a medium chain alcohol. A large number of publications describe the importance of MEs in many branches of chemistry, and there is an intensive search for new applications. In addition, MEs have been applied in many areas, including oil extraction, removal of environmental pollutants from soils and effluents, dissolution of additives in lubricants and cutting oils, cleaning processes, dyeing and textile finishing, as nanoreactors to obtain nanoparticles of metals, semiconductors, superconductors, magnetic and photographic materials, and latex. However, only some studies indicate the potential applications of MEs in food and even fewer evaluate their chemical behavior. Potential applications of MEs in food comprise dissolution of lipophilic additives, stabilization of nutrients and biologically active compounds, using as an antimicrobial agent and to maximize the efficiency of food preservatives. This work consists of a literature review focusing on composition and physical and chemical characteristics of microemulsions. Despite the small number of studies on the subject reported in the literature, we demonstrate some potential applications of MEs in food chemistry.

PRODUÇÃO DE BIODIESEL A PARTIR DE ÁCIDOS GRAXOS PROVENIENTES DO REFINO DE ÓLEOS VEGETAIS VIA CATÁLISE ÁCIDA HETEROGENEA E MICRO-ONDAS

This work presents the biofuel production results of the esterification of fatty acids (C12-C18) and high-acid-content waste vegetable oils from different soap stocks (soybean, palm, and coconut) with methanol, ethanol, and butanol by acid catalysis. We used Amberlyst-35 (A35) sulfonic resin as a heterogeneous acid catalyst and p-toluenesulfonic acid as a homogeneous catalyst for comparison. Both the heterogeneous (A35) and homogeneous (p-toluenesulfonic acid) reactions were performed with 5% w/w of catalyst. The final products were analyzed by proton nuclear magnetic resonance (1H NMR). The homogeneous catalyzed esterification of fatty acids with methanol, ethanol, and butanol produced esters with yields higher than 90%. In the reaction with fatty acids and methanol catalyzed by A35, the best results were achieved with lauric acid and methanol, with a yield of 97%. An increase in the hydrocarbon chain decreased the rate of conversion and yield for stearic acid with methanol, which was 90%. Maximum biodiesel production was achieved from coconut and soybean soap stocks and methanol (96%-98%), which showed conversions very close to those obtained from their respective fatty acids. Microwave irradiation reduced the reaction time from 6 to 1 h in the esterification reaction of fatty acids with butanol.

DESENVOLVIMENTO DE UMA TÉCNICA ULTRASSÔNICA PARA AVALIAR TEORES DE ÓLEO E GRAXA EM EFLUENTES DE BIOCOMBUSTÍVEIS

Ultrasound as a metrology tool has many applications in health care, industrial, and chemical analyses. Ultrasonic techniques are rapid, low-cost, non-invasive, and highly repeatable. Although ultrasound can be used to measure emulsions, no effort had been made thus far to optimize its sensitivity for metrological analysis. In this work, a technique for analyzing oil in water was validated. The wave velocity and attenuation were chosen as the ultrasonic parameters. The technique was implemented in the boundary region established by law for effluents from industrial plants involved with biofuel manufacturing. A technical effort of this study was to establish stable emulsions in concentrations close to the desired limit of study. The phase behaviours of pseudo-ternary oil, sodium chloride, and sodium lauryl sulphate were studied. The composition in the widest region of the diagram allowed for the formation of a stable emulsion, from which the ultrasound measurement was carried out. An analytical curve was obtained using ultrasonic attenuation to determine the content of oils and greases in wastewater ranging 15–240 ppm. The speed of sound did not appear to be an applicable parameter for this application. The technique was demonstrated to be an important alternative solution for the continuous monitoring of wastewater with regard to oil concentrations.

DESENVOLVIMENTO DE ENSAIO PARA ANÁLISE QUALITATIVA DE BIODIESEL EM MISTURAS DIESEL-BIODIESEL PARA APLICAÇÃO EM POSTOS REVENDEDORES DE COMBUSTÍVEIS

In this study, we developed a method for the visual detection of biodiesel in petrodiesel-biodiesel (BX) blends through the aminolysis of the methyl or ethyl esters of fatty acids that are found in biodiesel and that are absent from diesel and vegetable oils. This method is based on three reactional stages, which produce a dark red and easily visualized complex in the presence of biodiesel. In the absence of biodiesel, there is no dark red coloring, whereas in the presence of diesel or vegetable oil, there is a light red to yellow coloring. This simple, practical, inexpensive, and effective procedure may be applied by petrol stations to guarantee to consumers and resellers the presence of biodiesel in diesel blends, regardless of the BX blend's initial coloring or of the sulfur found in the diesel. In short, it ensures a safe fuel tank fill-up with BX blend.

Identification of the major fungitoxic component of cinnamon bark oil

The study was done to identify the most active fungitoxic component of cinnamon bark (Cinnamomum zeylanicum) oil that can be used as a marker for standardization of cinnamon extract or oil based natural preservative of stored seeds. Aspergillus flavus and A. ruber were used as test fungi. The hexane extracted crude oil and the hydro-distilled essential oil from cinnamon bark had complete growth inhibition concentration (CGIC) of 300 and 100 µl/l, respectively. Both oils produced three fractions on preparative thin layer silica-gel chromatography plates. The fraction-2 of either oil was the largest and most active, with CGIC of 200 µl/l, but the fungitoxicity was also retained in the other two fractions. The fraction-1 and 3 of the crude oil reduced growth of both the fungal species by 65%, and those of distilled oil by 45% at 200 µl/l. The CGIC of these fractions from both the sources was above 500 µl/l. The gas chromatography and mass spectrometry (GC-MS) of the fraction-2 of the hexane extract revealed that it contained 61% cinnamaldehyde, 29% cinnamic acid, and two minor unidentified compounds in the proportion of 4% and 6%. The GC-MS of the fraction-2 of the distilled oil revealed that it contained 99.1% cinnamaldehyde and 0.9% of an unidentified compound. The CGIC of synthetic cinnamaldehyde was 300 µl/l and that of cinnamic acid above 500 µl/l. The 1:1 mixture of cinnamaldehyde and cinnamic acid had CGIC of 500 µl/l. The data revealed that cinnamaldehyde was the major fungitoxic component of hexane extract and the distilled essential oil of cinnamon bark, while other components have additive or synergistic effects on total fungitoxicity. It is suggested that the natural seed preservative based on cinnamon oil can be standardized against cinnamaldehyde.

Production of biodiesel from babassu oil using methanol-ethanol blends

Maranhão state in Brazil presents a big potential for the cultivation of several oleaginous species, such as babassu, soybean, castor oil plant, etc... These vegetable oils can be transformed into biodiesel by the transesterification reaction in an alkaline medium, using methanol or ethanol. The biodiesel production from a blend of these alcohols is a way of adding the technical and economical advantages of methanol to the environmental advantages of ethanol. The optimized alcohol blend was observed to be a methanol/ethanol volume ratio of 80 % MeOH: 20 % EtOH. The ester content was of 98.70 %, a value higher than the target of the ANP, 96.5 % (m/m), and the biodiesel mass yield was of 95.32 %. This biodiesel fulfills the specifications of moisture, specific gravity, kinematic viscosity and percentages of free alcohols (methanol plus ethanol) and free glycerin.

Adsorption isotherm studies of BOD, TSS and colour reduction from palm oil mill effluent (POME) using boiler fly ash

Palm oil is one of the two most important vegetable oils in the world's oil and fats market. The extraction and purification processes generate different kinds of waste generally known as palm oil mill effluent (POME). Earlier studies had indicated the possibility of using boiler fly ash to adsorb impurities and colour in POME treatment. The adsorption treatment of POME using boiler fly ash was further investigated in detail in this work with regards to the reduction of BOD, colour and TSS from palm oil mill effluent. The amount of BOD, colour and TSS adsorbed increased as the weight of the boiler fly ash used was increased. Also, the smaller particle size of 425µm adsorbed more than the 850µm size. Attempts were made to fit the experimental data with the Freundlich, Langmuir and Dubinin-Radushkevich isotherms. The R² values, which ranged from 0.8974-0.9898, 0.8848-0.9824 and 0.6235-0.9101 for Freundlich, Langmuir and Dubinin-Radushkevich isotherms respectively, showed that Freundlich isotherm gave a better fit followed by Langmuir and then Dubinin-Radushkevich isotherm. The sorption trend could be put as BOD > Colour > TSS. The apparent energy of adsorption was found to be 1.25, 0.58 and 0.97 (KJ/mol) for BOD, colour and TSS respectively, showing that sorption process occurs by physiosorption. Therefore, boiler fly ash is capable of reducing BOD, Colour and TSS from POME and hence could be used to develop a good adsorbent for POME treatment.