Desarrollo de un modelo SIMCA para la clasificación de kerosinas mediante el empleo de la espectroscopía infrarroja

In the petroleum refining industry, the use of crude from several origins is frequent. This leads to a product of variable chemical composition during refining, hindering quality control. Therefore, it is important to develop classification models that help to better characterize those products. The objective of this study is to develop a SIMCA recognition pattern to classify kerosene using infrared spectroscopy data. The model permits to differentiate two kerosene groups with different chemical compositions, which was corroborated by mass spectrometry.

Validation of an analytical methodology for the quantitative analysis of petroleum hydrocarbons in marine sediment samples

This work describes a validation of an analytical procedure for the analysis of petroleum hydrocarbons in marine sediment samples. The proposed protocol is able to measure n-alkanes and polycyclic aromatic hydrocarbons (PAH) in samples at concentrations as low as 30 ng/g, with a precision better than 15% for most of analytes. The extraction efficiency of fortified sediments varied from 65.1 to 105.6% and 59.7 to 97.8%, for n-alkanes and PAH in the ranges: C16 - C32 and fluoranthene - benzo(a)pyrene, respectively. The analytical protocol was applied to determine petroleum hydrocarbons in sediments collected from a marine coastal zone.

Avaliação cinética da produção de biossurfactantes bacterianos

Biosurfactants present advantages in relation to the synthetic surfactants, as the biodegradability and low toxicity, and can be applied in the food industry, in pharmaceutical products, cosmetics and in the petroleum recovery. This paper aimed at selecting bacteria for biosurfactant production, evaluating the surface tension and the emulsifying activity and studying the fermentation process kinetics. The pure culture of Corynebacterium aquaticum showed capacity to promote emulsions formation and presented the smallest surface tension (28.8 mN m-1), and, in general, larger kinetic parameters, being selected as biosurfactant producer.

Determination of polyphenol contents and antioxidant capacity of no-alcoholic red grape products (vitis labrusca) from conventional and organic crops

The polyphenol contents and antioxidant capacity of Brazilian red grape juices and wine vinegars were analyzed. Additionally, it was analyzed the human polyphenol absorption and acute effect in plasmatic oxidative metabolism biomarkers after juice ingestion. The organic Bordo grape juice (GBO) presented a higher level of trans-resveratrol, quercitin, rutin, gallic acid, caffeic acid and total flavonoids then other juices and vinegars as well as antioxidant capacity. The plasmatic polyphenol increased 27.2% after GBO juice ingestion. The results showed that juices and vinegars from Brazilian crops present similar chemical and functional properties described in studies performed in other countries.

Development of a flotation-spectrophotometric method for determination of cetylpyridinium chloride in pharmaceutical products

A new simple and sensitive flotation-spectrophotometric method for the determination of cetylpyridinium chloride (CPC) is reported. The method is based on the formation of an ion- associate between CPC and Orange II (OR) which is floated in the interface of aqueous phase and n-hexane by vigorous shaking. The aqueous solution was discarded and the adsorbed ion associate on to the wall of a separating funnel was dissolved in a small volume of methanol solvent and its absorbance was measured at 480 nm. The apparent molar absorptivity (Ε) of the ion associate was determined to be 4.12 x 10(5) L mol-1 cm-1. The calibration graph was linear in the concentration range of 15-800 ng mL-1 of CPC with a correlation coefficient of 0.9988. The limit of detection (LOD) was 10.8 ng mL-1. The relative standard deviation (RSD) for determination of 100 and 800 ng mL-1 of CPC was 3.47 and 2.04% (n=7), respectively. The method was successfully applied to the determination of CPC in a commercial mouth washer product.

Isolation and quantitative HPLC-PDA analysis of lupeol in phytopharmaceutical intermediate products from Vernonanthura ferruginea (Less.) H. Rob.

Prior to obtain a standardized dried extract from V. ferruginea, lupeol was first time isolated from leaves and used as chemical maker. An analytical method using HPLC-PDA for lupeol determination in V. ferruginea intermediate products was developed using a C8 reverse-phase column, acetonitrile-acetic acid (99.99:0.01, v/v) as mobile phase at 0.8 mL min-1, oven temperature at 23-25 ºC, sample injection volume at 30 µL and detection at 210 nm. The method presented linearity from 10 to 160 µg mL-1, accuracy, precision, robustness and suitable sensitivity proving to be a useful tool to the obtainment process of lupeol standardized dried extracts of V. ferruginea.

New strategies for treatment and reuse of spent sulfidic caustic stream from petroleum industry

This work examines traditional and new routes for removal of H2S and other sulfur compounds from spent sufidic caustic (SSC). SH- (hydrogenosulfide) and S2- (sulfide) ions were quantitatively oxidized at 25 ºC using H2O2, NaOCl or a spent sulfochromic mixture. SH-/S2- ions were also removed via reaction with freshly prepared iron or manganese hydroxides, or after passing the SSC through strong basic anion exchange resins (OH- form). The treated caustic solution, as well as iron/manganese hydroxides, removed H2S from diesel samples at 25 ºC. SSC treatment via strong basic anion-exchange resins produced the treated caustic solution with the highest free alkalinity.

Straightforward synthesis of 2,2,4,4,5,7,7-d7-cholestane: a new deuterated standard in petroleum analysis

A short and efficient synthesis of heptadeuterated 2,2,4,4,5,7,7-d7-cholestane (1) from cholesterol (3) is described. The deuterated material will be useful for the analysis of different sources of petroleum in analytical geochemistry laboratories as internal standard for quantification of steranes via gas chromatography-mass spectrometry (GC-MS).

Química e sustentabilidade: novas fronteiras em biocombustíveis

This contribution discusses the state of the art and the challenges in producing biofuels, as well as the need to develop chemical conversion processes of CO2 in Brazil. Biofuels are sustainable alternatives to fossil fuels for providing energy, whilst minimizing the effects of CO2 emissions into the atmosphere. Ethanol from fermentation of simple sugars and biodiesel produced from oils and fats are the first-generation of biofuels available in the country. However, they are preferentially produced from edible feedstocks (sugar cane and vegetable oils), which limits the expansion of national production. In addition, environmental issues, as well as political and societal pressures, have promoted the development of 2nd and 3rd generation biofuels. These biofuels are based on lignocellulosic biomass from agricultural waste and wood processing, and on algae, respectively. Cellulosic ethanol, from fermentation of cellulose-derived sugars, and hydrocarbons in the range of liquid fuels (gasoline, jet, and diesel fuels) produced through thermochemical conversion processes are considered biofuels of the new generation. Nevertheless, the available 2nd and 3rd generation biofuels, and those under development, have to be subsidized for inclusion in the consumer market. Therefore, one of the greatest challenges in the biofuels area is their competitive large-scale production in relation to fossil fuels. Owing to this, fossil fuels, based on petroleum, coal and natural gas, will be around for many years to come. Thus, it is necessary to utilize the inevitable CO2 released by the combustion processes in a rational and economical way. Chemical transformation processes of CO2 into methanol, hydrocarbons and organic carbonates are attractive and relatively easy to implement in the short-to-medium terms. However, the low reactivity of CO2 and the thermodynamic limitations in terms of conversion and yield of products remain challenges to be overcome in the development of sustainable CO2 conversion processes.

USE OF A LOW-COST TEMPLATE-FREE ZSM-5 FOR ATMOSPHERIC PETROLEUM RESIDUE PYROLYSIS

To understand the physicochemical properties and catalytic activity during the pyrolysis of atmospheric petroleum residue, a template-free ZSM-5 zeolite was synthesized using a direct method without additional seeds or an organic structure director and compared with conventionally synthesized ZSM-5. The crystallinities of the two zeolites were evaluated by XRD and FTIR and were quite similar; however, structural analyses using SEM and argon physisorption revealed that the zeolites diverged in particle diameter and in the external surface area of the micropores. The synthesis procedure without a template incorporated additional aluminum into the crystalline network, according to ICP-AES and TPD NH3 experiments. The catalytic pyrolysis performed over the template-free ZSM-5 generated results comparable to those for pyrolysis performed over the conventional ZSM-5 according to its hydrocarbon distribution. The selectivity to aromatics compounds was exactly the same for both ZSM-5 zeolites, and these values stand out compared to thermal pyrolysis. The template-free ZSM-5 produced 20% of light hydrocarbons (C4-C6), where such compounds are olefins and paraffins of great interest to the petrochemical industry. Therefore, template-free ZSM-5 is promising for industrial use due to its lowered synthesis time, low-cost and significant distribution to light hydrocarbons.

Immunolocalisation of secreted-excreted products of Meloidogyne spp. using polyclonal and monoclonal antibodies

Molecules expressed at the surface cuticle (SC) of plant parasitic nematodes represent the primary plant-nematode interface, and together with secreted-excreted (S-E) products are probably the first signals perceived by the host. These molecules, which are released into plant tissue, probably play important roles in the host-parasite interactions. Characterisation of these antigens will help in the identification of nematode targets useful for novel control strategies, which interfere with the nematode infection of plants. Three monoclonal (MAbs) and three polyclonal (PAbs) antibodies produced to S-E products of Meloidogyne spp. and Heterodera avenae were used to examine their reactivity towards M. incognita and/or M. arenaria second stage juveniles and adult females. The three PAbs showed cross-reactivity with M. incognita and M. arenaria. Antibody Roth-PC 373 strongly recognised molecules present in the SC, amphids and intestine, antibody Roth-PC 389 recognised the nematode amphids and metacorpus, while antibody Roth-PC 419 bound to molecules present in the subventral glands. Reactivity of the MAbs was only tested against M. arenaria. Monoclonal antibody Roth-MAb T116C1.1 showed intense reactivity with molecules present in the amphidial and phasmidial glands. Monoclonal antibodies Roth-MAb T46.2 and T42D.2 labeled the nematode amphids and molecules present in the nematode oesophagus (metacorpus), respectively.

Avaliação do desempenho analítico do método de determinação de TPH (Total Petroleum Hydrocarbon) por detecção no infravermelho

No presente trabalho os parâmetros de desempenho (validação intralaboratorial) da metodologia de determinação de TPH (Total Petroleum Hydrocarbons) foram determinados por detecção na região do infravermelho com o equipamento da Infracal TOG/TPH, visando aplicação em amostras de areia contaminadas com petróleo. Os ensaios foram realizados utilizando Óleo Marine Fuel 380, com densidade igual 0,987 g cm-3 e viscosidade de 5313 cP a 20°C. Este óleo foi fornecido pelo Centro de Pesquisa da Petrobrás (CENPES/PETROBRÁS/RJ), sendo o mesmo óleo derramado no acidente ocorrido em janeiro de 2000, na Baia de Guanabara, RJ, quando 1.300 m3 vazaram do duto que interliga a REDUC (Refinaria Duque de Caxias, RJ) ao terminal da Ilha d’Água/RJ, atingindo praias. Os resultados da validação indicaram que o desempenho da metodologia foi favorável à aplicação que se destina. Entre os parâmetros metrológicos obtidos neste trabalho, o limite de detecção do método foi de 4,06 mg L-1, consideravelmente inferior à faixa de concentração normalmente obtida para amostras em tais situações.

Control system for forced-air cooling of horticultural products

This work is a study of the implementation of a classical controller using a tuning method referred to as IMC (Internal Model Control) and aimed at the reduction of electrical energy consumption by the appropriate relation between energy consumption and the cooling time with forced air. The supervisory system installed was able to manipulate the variable of frequency of the signal power of the exhaust fan engine (forced air module), to accelerate or decelerate the loss of heat from the product to be cooled by airflow variation that passes through the mass of the produce. The results demonstrated a reduction in energy consumption from 64% and an increase of only 8% in the cooling time to the system using PI/IMC (Proportional - Integral with IMC) tuning method compared with the system in its operating nominal condition. This PI/IMC control may be implemented directly in a frequency converter, without the need to purchase a computer or PLC (programmable logic controller) to run the dedicated application, increasing its economical viability.

Seasonality of net radiation in two sub-basins of Paracatu by the use of modis sensor products

The net radiation (Rn) represents the main source of energy for physical and chemical processes that occur in the surface-atmosphere interface, and it is used for air and soil heating, water transfer, in the form of vapor from the surface to the atmosphere, and for the metabolism of plants, especially photosynthesis. If there is no record of net radiation in certain areas, the use of information is important to help determine it. Among them we can highlight those provided by remote sensing. In this context, this work aims to estimate the net radiation, with the use of products of MODIS sensor, in the sub-basins of Entre Ribeiros creek and Preto River, located between the Brazilian states of Goiás and Minas Gerais. The SEBAL (Surface Energy Balance Algorithm for Land) was used to obtain the Rn in four different days in the period of July to October, 2007. The Rn results obtained were consistent with others cited in the literature and are important because the orbital information can help determine the Rn in areas where there are not automatic weather stations to record the net radiation.

Biological evaluation of recombinant human erythropoietin in pharmaceutical products

The potencies of mammalian cell-derived recombinant human erythropoietin pharmaceutical preparations, from a total of five manufacturers, were assessed by in vivo bioassay using standardized protocols. Eight-week-old normocythemic mice received a single subcutaneous injection followed by blood sampling 96 h later or multiple daily injections with blood sampling 24 h after the last injection. Reticulocyte counting by microscopic examination was employed as the end-point using the brilliant cresyl blue or selective hemolysis methods, together with automated flow cytometry. Different injection schedules were investigated and dose-response curves for the European Pharmacopoeia Biological Reference Preparation of erythropoietin were compared. Manual and automated methods of reticulocyte counting were correlated with respect to assay validity and precision. Using 8 mice per treatment group, intra-assay precision determined for all of the assays in the study showed coefficients of variation of 12.1-28.4% for the brilliant cresyl blue method, 14.1-30.8% for the selective hemolysis method and 8.5-19.7% for the flow cytometry method. Applying the single injection protocol, a combination of at least two independent assays was required to achieve the precision potency and confidence limits indicated by the manufacturers, while the multiple daily injection protocol yielded the same acceptable results within a single assay. Although the latter protocol using flow cytometry for reticulocyte counting gave more precise and reproducible results (intra-assay coefficients of variation: 5.9-14.2%), the well-characterized manual methods provide equally valid alternatives for the quality control of recombinant human erythropoietin therapeutic products.