Screening Brazilian commercial gasoline quality by hydrogen nuclear magnetic resonance spectroscopic fingerprintings and pattern-recognition multivariate chemometric analysis

The identification of gasoline adulteration by organic solvents is not an easy task, because compounds that constitute the solvents are already in gasoline composition. In this work, the combination of Hydrogen Nuclear Magnetic Resonance ((1)H NMR) spectroscopic fingerprintings with pattern-recognition multivariate Soft Independent Modeling of Class Analogy (SIMCA) chemometric analysis provides an original and alternative approach to screening Brazilian commercial gasoline quality in a Monitoring Program for Quality Control of Automotive Fuels. SIMCA was performed on spectroscopic fingerprints to classify the quality of representative commercial gasoline samples selected by Hierarchical Cluster Analysis (HCA) and collected over a 6-month period from different gas stations in the São Paulo state, Brazil. Following optimized the (1)H NMR-SIMCA algorithm, it was possible to correctly classify 92.0% of commercial gasoline samples, which is considered acceptable. The chemometric method is recommended for routine applications in Quality-Control Monitoring Programs, since its measurements are fast and can be easily automated. Also, police laboratories could employ this method for rapid screening analysis to discourage adulteration practices. (C) 2010 Elsevier B.V. All rights reserved.

Development, optimization and validation of gas chromatographic fingerprinting of Brazilian commercial gasoline for quality control

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Screening Brazilian Commercial Gasoline Quality by ASTM D6733 GC and Pattern-Recognition Multivariate SIMCA Chemometric Analysis

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

(1)H NMR Fingerprinting of Brazilian Commercial Gasoline: Pattern-Recognition Analyses for Origin Authentication Purposes

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Desempenho de um motor de trator agrícola em bancada dinamométrica com biodiesel de óleo de frango e misturas binárias com óleo diesel

O Brasil, terceiro maior produtor de biodiesel do mundo e terceiro maior produtor mundial de frango, pode incrementar, na sua matriz energética, o uso de óleo oriundo de aves como alternativa aos combustíveis fósseis e à redução da dependência do óleo de soja para esse fim. O país dispõe de mais de 350 milhões de litros de óleo de frango por ano. Considerando a aplicação dos combustíveis alternativos para os motores a diesel, em máquinas agrícolas, o trabalho teve por objetivo avaliar o desempenho do motor de um trator agrícola de 53kW acoplado pela TDP em bancada dinamométrica, operando com biodiesel metílico de óleo de frango e misturas com óleo diesel, sendo: B5 (testemunha), B20, B40, B60, B80 e B100. Avaliaram-se a potência, o torque, a reserva de torque, o consumo de combustível, o consumo de energia e a eficiência térmica do motor. O ensaio foi instalado com delineamento inteiramente casualizado (DIC) em esquema fatorial com seis tratamentos. Os resultados foram submetidos à análise de variância e as médias ajustadas por equações de regressão. Foram observadas perdas na geração de potência e torque, aumento no consumo de combustível, redução do consumo energético e melhoria na eficiência térmica do motor, de acordo com o aumento da proporção de biodiesel na mistura.

Increase on incineration capacity and NOx control for air enrichment in the experimental simulation of aqueous residue incineration

An experimental investigation of air enrichment in a combustion chamber designed to incinerate aqueous residues is presented. Diesel fuel and liquefied petroleum gas (LPG) were used independently as fuels. An increase of 85% in the incineration capacity was obtained with nearly 50% O-2 in the oxidant gas, in comparison to incineration with air only. The incineration capacity continues increasing for enrichment levels above 50% O-2 , although at a lower pace. For complete oxy-flame combustion (100% O-2 ), the increase of the incineration capacity was about 110% relative to the starting conditions and about 13.5% relative to the condition with 50% O-2 . The CO concentration measured near the flame front decreases drastically with the increase of O-2 content in the oxidant gas. At the chamber exit, the CO concentration was always near zero, indicating that the chamber residence time was sufficient to complete fuel oxidation in any test setting. For diesel fuel, the NOx was entirely formed in the first region of the combustion chamber. For diesel fuel, there was some increase in the NOx concentration up to 35% of O-2 ; this increase became very sharp after that. From 60 ppm, at operation with air only, the NOx concentration raises to 200 ppm at 35% O-2 , and then to 2900 ppm at 74% O-2 . The latter corresponds to six times more NOx in terms of the ratio of mass of NO to mass of residue, compared to the situation of combustion with air only. For LPG, the NOx concentrations reached 4200 ppm at 80% O-2 , corresponding to nine times more, also in terms of the ratio of mass of NO to mass of residue, in comparison with combustion with air only. Results of different techniques used to control the NOx emission during air enrichment are discussed: (a) variation of the recirculated zone intensity, (b) increase of the spray Sauter mean diameter, (c) fuel staging, (d) oxidizer staging, and (e) ammonia injection. The present paper shows that NOx emission may be controlled without damage of the increase of incineration capacity by the enrichment and with low emission of partial oxidation pollutants such as CO.

Simultaneous determination of quinoline and pyridine compounds in gasoline and diesel by differential pulse voltammetry

The presence of trace basic organonitrogen compounds such as quinoline and pyridine in derivative petroleum fuels plays an important role in maintaining the engines of vehicles. However, these substances can contaminate the environment and so must be controlled because most of them are potentially carcinogenic and mutagenic. For these reasons, a reliable and sensitive method was developed for the determination of basic nitrogen compounds in fuel samples such as gasoline and diesel. This method utilizes preconcentration on an ion-exchange resin (Amberlyte IR - 120 H) followed by differential pulse voltammetry (DPV) on a glassy carbon electrode. The electrochemical behavior of quinoline and pyridine as studied by cyclic voltammetry (CV) suggests that their reduction occurs via a reversible electron transfer followed by an irreversible chemical reaction. Very well resolved diffusion-controlled voltammetric peaks were obtained in dimethylformamide (DMF) with tetrabutylammonium tetrafluoroborate (TBAF(4) 0.1 mol L-1) for quinoline (-1.95 V) and pyridine (-2.52 V) vs. Ag vertical bar AgCl vertical bar KClsat reference electrode. The proposed DPV method displayed a good linear response from 0.10 to 300 mg L-1 and a limit of detection (LOD) of 5.05 and 0.25 mu g L-1 for quinoline and pyridine, respectively. Using the method of standard additions, the simultaneous determination of quinoline and pyridine in gasoline samples yielded 25.0 +/- 0.3 and 33.0 +/- 0.7 mg L-1 and in diesel samples yielded 80.3 +/- 0.2 and 131 +/- 0.4 mg L-1, respectively. Spike recoveries were 94.4 +/- 0.3% and 10 +/- 0.5% for quinoline and pyridine, respectively, in the fuel determinations. This proposed method was also compared with UV-vis spectrophotometric measurements. Results obtained for the two methods agreed well based on F and t student's tests.

Simultaneous determination of neutral nitrogen compounds in gasoline and diesel by differential pulse voltammetry

The presence of trace neutral organonitrogen compounds as carbazole and indole in derivative petroleum fuels plays an important role in the car's engine maintenance. In addition, these substances contribute to the environmental contamination and their control is necessary because most of them are potentially carcinogenic and mutagenic. For those reasons, a reliable and sensitive method was proposed for the determination of neutral nitrogen compounds in fuel samples, such as gasoline and diesel using preconcentration with modified silica gel (Merck 70-230 mesh ASTM) followed by differential pulse voltammetry (DPV) technique on a glassy carbon electrode. The electrochemical behavior of carbazole and indole studied by cyclic voltammetry (CV) suggests that their reduction occurs via a reversible electron transfer followed by an irreversible chemical reaction. Very well resolved diffusion controlled voltammetric peaks were obtained in dimethylformamide (DMF) with tetrabutylammonium tetrafluoroborate (TBAF(4) 0.1 mol L-1) for indole (-2.27 V) and carbazole (-2.67 V) versus Ag vertical bar AgCl vertical bar KClsat reference electrode. The proposed DPV method showed a good linear response range from 0.10 to 300 mg L-1 and a limit of detection (L.O.D) of 7.48 and 2.66 mu g L-1 for indole and carbazole, respectively. The results showed that simultaneous determination of indole and carbazole presents in spiked gasoline samples were 15.8 +/- 0.3 and 64.6 +/- 0.9 mg L-1 and in spiked diesel samples were 9.29 +/- 1 and 142 +/- 1 mg L-1, respectively. The recovery was evaluated and the results shown the values of 88.9 +/- 0.4 and 90.2 +/- 0.8% for carbazole and indole in fuel determinations. The proposed method was also compared with UV-vis spectrophotometric measures and the results obtained for the two methods were in good agreement according to the F and t Student's tests. (C) 2007 Elsevier B.V. All rights reserved.

Square-wave voltammetry applied to the analysis of the dye marker, solvent blue 14, in kerosene and fuel alcohol

The purpose of this paper is to develop an electroanalytical method based on square-wave voltammetry (SWV) for the determination of the solvent blue 14 (SB-14) in fuel samples. The electrochemical reduction of SB-14 at glassy carbon electrode in a mixture of Britton-Robinson buffer with N,N-dimethyiformamide (1:1, v/v) presented a well-defined peak at-0.40 V vs. Ag/AgCl. All parameters of the SWV technique were optimized and the electroanalytical method presented a linear response from 1.0 x 10(-6) to 6.0 x 10(-6) mol L-1 (r = 0.998) with a detection limit of 2.90 x 10(-7) mol L-1. The developed method was successfully utilized in the quantification of the dye SB-14 in kerosene and alcohol samples with average recovery from 93.00 to 98.10%.

Determination of the activation energies of beef tallow and crude glycerin combustion using thermogravimetry

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

A Review on the Challenges for Increased Production of Castor

Castor (Ricinus communis L.) is one of the oldest cultivated crops, but currently it represents only 0.15% of the vegetable oil produced in the world. Castor oil is of continuing importance to the global specialty chemical industry because it is the only commercial source of a hydroxylated fatty acid. Castor also has tremendous future potential as an industrial oilseed crop because of its high seed oil content (more than 480 g kg(-1)), unique fatty acid composition (900 g kg(-1) of ricinoleic acid), potentially high oil yields (1250-2500 L ha(-1)), and ability to be grown under drought and saline conditions. The scientific literature on castor has been generated by a relatively small global community of researchers over the past century. Much of this work was published in dozens of languages in journals that are not easily accessible to the scientific community. This review was conducted to provide a compilation of the most relevant historic research information and define the tremendous future potential of castor. The article was prepared by a group of 22 scientists from 16 institutions and eight countries. Topics discussed in this review include: (i) germplasm, genetics, breeding, biotic stresses, genome sequencing, and biotechnology; (ii) agronomic production practices, diseases, and abiotic stresses; (iii) management and reduction of toxins for the use of castor meal as both an animal feed and an organic fertilizer; (iv) future industrial uses of castor including renewable fuels; (v) world production, consumption, and prices; and (vi) potential and challenges for increased castor production.

Toxic effects of nickel exposure on heart and liver of rats

The role of air pollution as a health risk factor is of special interest. Numerous toxic pollutants, such as nickel, are being released to the environment as a result of combustion of fossil fuels, crude oil, and coal. Nickel in the atmosphere can be combined with other environmental pollutants, producing various nickel compounds, which have varying animal toxicity. A rat biossay validated for the identification of toxic effects of nickel revealed increased serum activities of total lactate dehydrogenase (LDH) and alanine transaminase (ALT) in rats that received intratracheal injection of Ni2+ in .09% saline solution of NiCl2. The total LDH activity was also increased in the heart, and the isoenzyme pattern showed the LDH1/LDH2 ratio elevated to greater than 1. We conclude that intratracheal administration of nickel induced cardiac and hepatic damage. The development of cardiac and hepatic damage and of increased enzymes' activities was only demonstrated when nickel had accumulated in these tissues, indicating that nickel depot is essential to its toxicity. Intratracheal administration of NiCl2 induced changes in LDH and ALT activities.

Análise térmica do processo de incineração de resíduos aquosos com chamas enriquecidas

The use of oxygen to enrich the combustion air can be an attractive technique to increase capacity of an incinerator originally designed to operate with air. If incinerator parameters such as operation temperature, turbulence level and residence time are fixed for a certain fuel supply rate, it is possible to increase the residue consumption rate using enriched air. This paper presents the thermal analysis for operation with enriched air of an aqueous residue experimental incinerator. The auxiliary fuel was diesel oil. The theoretical results showed that there is a considerable increase in the incineration ratio up to approximately 50 % of O 2 in the oxidiser. The tendency was confirmed experimentally. Thermal analysis was demonstrated to be an important tool to predict possible incinerator capacity increase.

Windrowing and prismatic baling of sugar cane vegetal residues: Some operational parameters and energetic efficiency

It was evaluated the energetic efficiency and operational parameters of a windrowing and prismatic baling, both from CASE NEW HOLLAND® operations in sugarcane vegetal residues (green leaves, dry leaves and tops) picked mechanically in green cane. The area belongs to COSTA PINTO MILL (COSAN® Group) which was harvested mechanically by combines in the State of Sao Paulo, Brazil. The geographic location of the area is: Latitude 22°40'30S, Longitude 47°36'38W and Altitude of 605m. The variety was RB 82-5336, planted in 1.40m row spacing, with 78t.ha-1 yield. The vegetal residues analysis obtained 69.93% of leaves, 21.44% of stalks fractions, 2.27% of tops and 6.36% of total strange matter. The vegetal residues values were: gross heat of 18.43MJ.kg-1, low heat of 17.00MJ.kg'1 and useful heat of 12.94MJ.kg-1. The vegetal residues average energetic potential was 342.48GJ.ha-1. The treatments were simple, double and triple windrowing. The use of the rake and prismatic baler to pick up the residues was viable. The simple windrowing treatment presented the best results: effective capacity of 83.06t.ha-1, fuel consumption of 0.18L.t -1 and 99.95% of positive energetic efficiency. The bales obtained in the treatment of triple windrowing presented the largest specific mass average of 221.11kg.m-3. The soil amount in the bales increased with successive windrowing. The baling operation in the triple windrowing treatment obtained better results, presenting the effective capacities of 20.29t.h -1 and 1.45ha.h-1 and fuel consumption of for baled in 1.37L.t-1. The high total energetic efficiency of 99.53% indicates that is technically viable the withdrawal of the vegetal residues.