Fotodegradação de hidrocarbonetos policíclicos aromáticos em placas de sílica impregnadas com dióxido de titânio

Photodegradation of the PAHs anthracene, chrysene and benzo[k]fluoranthane on silica gel impregnated with TiO2 and over glass plates holding TiO2 was studied. Silica gel plates holding these substances were exposed to solar radiation, developed with hexane and photographed under ultra-violet light. The plates containing benzo[k]fluoranthene were also analysed by both diffuse reflectance and laser induced fluorescence. Diffuse reflectance spectra of the fluorescent spot from non irradiated plates showed small differences when compared with those obtained from irradiated plates. These spectral differences are compatible with formation of less conjugated compounds during irradiation. Fluorescence and time resolved fluorescence spectra observed after irradiation were identical to those obtained with benzo[k]fluoranthene in methanol. On plates holding silica, PAH degradation requires longer periods of solar irradiation when compared with those plates containing silica impregnated with TiO2. Glass plates impregnated with TiO2 also showed very rapid PAH degradation.

A destilação simulada na indústria do petróleo

One of the most widely used physico-chemical characterizations of hydrocarbon mixtures is the determination of their boiling point distribution. Knowledge of the boiling range of crude oils and petroleum products is essential to ensure the correct specification of final products and to control refinery processes. Simulated distillation, a GC based process, has been playing this role for the past decades in the petroleum industry. The main purpose of this work is to show the fundamentals of this technique as well as its present trends.

Determinação das formas de nitrogênio e nitrogênio total em rochas-reservatório de petróleo por destilação com arraste de vapor e método do indofenol

Several extraction procedures are described for the determination of exchangeable and fixed ammonium, nitrate + nitrite, total exchangeable nitrogen and total nitrogen in certified reference soils and petroleum reservoir rock samples by steam distillation and indophenol method. After improvement of the original distillation system, an increase in worker safety, a reduction in time consumption, a decrease of 73% in blank value and an analysis without ammonia loss, which could possibly occur, were achieved. The precision (RSD < 8%, n = 3) and the detection limit (9 mg kg-1 NH4+-N) are better than those of published procedures.

Determinação de hidrocarbonetos voláteis e semi-voláteis na atmosfera

This paper focuses: (i) the development of a measurement technique for the determination of atmospheric C2-C6 hydrocarbons with sampling in canisters and analysis by gas chromatography/flame ionisation detector (GC/FID), (ii) the improvement of an existent adsorption-sampling technique with Tenax TA tubes for the determination of C6-C11 hydrocarbons and analysis by GC/FID after thermal desorption and cryogenic concentration, (iii) the identification of compounds present in ambient air by gas chromatography/mass spectrometry (GC/MS) for both canister and Tenax samples, (iv) a program of interlaboratorial comparison for quality control of C2-C11 analyses, and (v) the seasonal characterisation of ambient air C2-C11 hydrocarbons.

Desempenho de biomassas na adsorção de hidrocarbonetos leves em efluentes aquosos

Removal of hydrocarbons from aqueous effluents using biosorbents was investigated. The effluent was simulated by a dispersion of gasoline (simple hydrocarbons) in water. Corn-cob, wood powder, coconut mesocarp and sugar-cane bagasse were used as adsorbents and their performance verified by means of batch experiments performed in an agitated vessel. The influence of input variables such as hydrocarbon concentration, mass of biomass and agitation level on the adsorbents' capacity was studied by means of factorial design. The results indicated that, among the materials studied, coconut mesocarp and sugar-cane bagasse can be considered promising biomasses for treating aqueous effluents contaminated by hydrocarbons.

Utilização da extração em fase sólida (SPE) na determinação de hidrocarbonetos policíclicos aromáticos em matrizes aquosas ambientais

Polycyclic aromatic hydrocarbons (PAHs) are a great environmental concern mainly because of their toxic, mutagenic and carcinogenic potential. This paper reports utilization of the solid-phase extraction (SPE) technique to determine PAHs in environmental aqueous matrices. The recovery from environmental aqueous matrices fortified with PAHs varied from 63.7 to 93.1% for atmospheric liquid precipitation, from 38.3 to 95.1% for superficial river water, and from 71.0 to 95.5% for marine water. No negative matrix effect was observed for the recovery of PAHs from atmospheric liquid precipitation and marine water, but was observed for superficial river water, particularly for PAHs possessing 5 and 6 aromatic rings.

Hidrocarbonetos policíclicos aromáticos como traçadores da queima de cana-de-açúcar: uma abordagem estatística

In this study atmospheric particulates of PAHs were measured in Araraquara, Piracicaba and São Paulo in July 2003 (sugarcane harvest season in Araraquara and Piracicaba) and in Araraquara in March of 2003. The results were normalized to the total PAH concentrations. Comparison among the sites and principal component analysis (PCA) were used to investigate possible tracers of emission. Fluoranthene and pyrene concentrations were higher in Piracicaba and Araraquara samples. These PAH were also responsible for the largest negative loadings on the second principal component and account for the negative scores and for the formation of the Araraquara and Piracicaba group.

Utilização de solos locais para tratamento de efluentes do refino de petróleo contendo metais

The employment of local soils for extraction of metallic elements was evaluated through batch tests to treat wastewaters generated in a petroleum refinery plant in southern Brazil. Clay and organic carbon content and clay mineralogy provide these soils, in principle, with moderate metal retention capacity. The following retention order was established: Cr3+ > Pb2+ > Cu2+ > Hg2+ > Cd2+, with total amount of metals retained varying from 36 to 65 meq kg-1. The results show the high efficiency of local soils for extracting metals from liquid effluents through sorption and precipitation processes under acid pH conditions.

Contaminação de aqüífero por hidrocarbonetos: estudo de caso na Vila Tupi, Porto Velho - Rondônia

Underground storage tanks (UST) are widely used in the Porto Velho area. A large number of these USTs are in bad condition due to corrosion processes causing groundwater contamination. A large number of these leaking underground fuel tanks (LUFT) are in urban areas but due to the lack of water quality monitoring, they are only detected when there is a high contamination level. This study identified petroleum hydrocarbons, derived from a LUFT, by a silica gel/petroleum ether partitioning gravimetric method and by gas chromatographic analysis of samples collected in wells dug in a gas station and in houses in the aforementioned neighborhood.

Remoção do íon amônio de águas produzidas na exploração de petróleo em áreas offshore por adsorção em clinoptilolita

This work describes the use of clinoptilolite for removal of ammonium ions present in waters produced at the Campos' Basin. Samples were previously treated in order to remove organic compounds and metals. Experiments were run in fixed- and fluidized-bed systems, at room temperature. The fluidized-bed systems did not remove efficiently the ammonium ion. The best operational conditions were obtained with clinoptilolite particle size in the range 0.30-0.50 mm, under ascendant flow (3 mL min-1), in a fixed-bed system. The best zeolite performance was found when it was pretreated with 0.5 mol L-1 NaOH. Na+ was the most important interfering ion due to its high concentration in the water. Clinoptilolite lost partially its capacity to retain ammonium ions after several regeneration cycles with NaOH.

Técnicas de extrações e procedimentos de clean-up para a determinação de hidrocarbonetos policílicos aromáticos (HPA) em sedimentos da costa do Ceará

Extraction and clean-up are essential points in polycyclic aromatic hydrocarbon (PAHs) analysis in a solid matrix. This work compares extraction techniques and clean-up procedures for PAH analysis. PAH levels, their toxicological significance and source were also evaluated in the waters of the Cocó and Ceará rivers. The efficiency of PAH recovery was higher for the soxhlet and ultrasonic techniques. PAH recovery varied from 69.3 to 99.3%. Total PAH concentration (ΣHPA) varied from 720.73 to 2234.76 µg kg-1 (Cocó river) and 96.4 to 1859.21 µg kg-1 (Ceará river). The main PAH sources are pyrolytic processes and the levels were classified as medium so that adverse effects are possible.

Principais aplicações das microondas na produção e refino de petróleo

Microwave irradiation offers a clean, inexpensive, and convenient method of heating, which is an alternative way of introducing energy into chemical systems. In particular, applications of microwave irradiation technology for petroleum processing have been developed in the last twenty years. The main objective of this paper is to review the use of microwave irradiation technology as an alternative technique applied during petroleum refining and primary processing of petroleum fluids, presenting and discussing successful applications of this technology as a tool for petroleum emulsion separation and catalytic reactions normally found at hydrorefining plants.

Co-produção de lipase e biossurfactante em estado sólido para utilização em biorremediação de óleos vegetais e hidrocarbonetos

Recently lipases have been increasing in prominence due to its wide industrial application. The lipase production can be influenced by different variables such as the producing microorganism, carbon sources, aeration and agitation conditions, inductor type and the geometry of the reactor. Biosurfactants are composites of surface active produced by microbial cells which reduce superficial and interfacial tensions. The objective of this study was to verify the influence of different process variables in the lipase production during a fermentative process. The results showed that the concomitant production of lipases and biosurfactant was possible in different cultivation conditions.

Adsorção competitiva de inibidor de corrosão usado em poços de perfuração de petróleo sobre aço, esmectita e arenito

A commercial corrosion inhibitor used in petroleum production was characterized by means of infrared spectroscopy and energy dispersive spectroscopy (EDS). Predicting the adsorption behavior of corrosion inhibitor onto steel, sandstone and esmectite is the key to improve working conditions. In this study, the adsorption kinetics of inhibitor formulations in HCl 15% or in Mud Acid (HCl 13,5% and ammonium bifluoride) onto steel, sandstone and esmectite was determined by means of spectrophotometry. Kinetic parameters indicated that adsorption of inhibitor in the presence of bifluoride was favored. Moreover, the adsorption constant rate was the largest when the substrate was esmectite.

Hidrocarbonetos policíclicos aromáticos (HPAS) em cachaça, rum, uísque e álcool combustível

The concentration of 15 polycyclic aromatic hydrocarbons (PAHs) in 57 samples of distillates (cachaça, rum, whiskey, and alcohol fuel) has been determined by HPLC-Fluorescence detection. The quantitative analytical profile of PAHs treated by Partial Least Square - Discriminant Analysis (PLS-DA) provided a good classification of the studied spirits based on their PAHs content. Additionally, the classification of the sugar cane derivatives according to the harvest practice was obtained treating the analytical data by Linear Discriminant Analysis (LDA), using naphthalene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benz[a]anthracene, benz[b]fluoranthene, and benz[g,h,i]perylene, as a chemical descriptors.