Novas alternativas de remoção de enxofre do óleo diesel utilizando tensoativos e microemulsões

The diesel combustion form sulfur oxides that can be discharged into the atmosphere as particulates and primary pollutants, SO2and SO3, causing great damage to the environment and to human health. These products can be transformed into acids in the combustion chamber, causing damage to the engines. The worldwide concern with a clean and healthy environment has led to more restrictive laws and regulations regulating the emission levels of pollutants in the air, establishing sulfur levels increasingly low on fuels. The conventional methods for sulfur removal from diesel are expensive and do not produce a zero-level sulfur fuel. This work aims to develop new methods of removing sulfur from commercial diesel using surfactants and microemulsion systems. Its main purpose is to create new technologies and add economic viability to the process. First, a preliminary study using as extracting agent a Winsor I microemulsion system with dodecyl ammonium chloride (DDACl) and nonyl phenol ethoxylated (RNX95) as surfactant was performed to choose the surfactant. The RNX95 was chosen to be used as surfactant in microemulsioned systems for adsorbent surface modification and as an extracting agent in liquid-liquid extraction. Vermiculite was evaluated as adsorbent. The microemulsion systems applied for vermiculite surface modification were composed by RNX95 (surfactant), n-butanol (cosurfactant), n-hexane (oil phase), and different aqueous phases, including: distilled water (aqueous phase),20ppm CaCl2solution, and 1500ppm CaCl2solution. Batch and column adsorption tests were carried out to estimate the ability of vermiculite to adsorb sulfur from diesel. It was used in the experiments a commercial diesel fuel with 1,233ppm initial sulfur concentration. The batch experiments were performed according to a factorial design (23). Two experimental sets were accomplished: the first one applying 1:2 vermiculite to diesel ratio and the second one using 1:5 vermiculite to diesel ratio. It was evaluated the effects of temperature (25°C and 60°C), concentration of CaCl2in the aqueous phase (20ppm and 1500ppm), and vermiculite granule size (65 and 100 mesh). The experimental response was the ability of vermiculite to adsorb sulfur. The best results for both 1:5 and 1:2 ratios were obtained using 60°C, 1500ppm CaCl2solution, and 65 mesh. The best adsorption capacities for 1:5 ratio and for 1:2 ratio were 4.24 mg sulfur/g adsorbent and 2.87 mg sulfur/g adsorbent, respectively. It was verified that the most significant factor was the concentration of the CaCl2 solution. Liquid-liquid extraction experiments were performed in two and six steps using the same surfactant to diesel ratio. It was obtained 46.8% sulfur removal in two-step experiment and 73.15% in six-step one. An alternative study, for comparison purposes, was made using bentonite and diatomite asadsorbents. The batch experiments were done using microemulsion systems with the same aqueous phases evaluated in vermiculite study and also 20ppm and 1500 ppm BaCl2 solutions. For bentonite, the best adsorption capacity was 7.53mg sulfur/g adsorbent with distilled water as aqueous phase of the microemulsion system and for diatomite the best result was 17.04 mg sulfur/g adsorbent using a 20ppm CaCl2solution. The accomplishment of this study allowed us to conclude that, among the alternatives tested, the adsorption process using adsorbents modified by microemulsion systems was considered the best process for sulfur removal from diesel fuel. The optimization and scale upof the process constitutes a viable alternative to achieve the needs of the market

Combined cycle versus one thousand diesel power plants: pollutant emissions, ecological efficiency and economic analysis

The increase in the use of natural gas in Brazil has stimulated public and private sectors to analyse the possibility of using combined cycle systems for generation of electrical energy. Gas turbine combined cycle power plants are becoming increasingly common due to their high efficiency, short lead times, and ability to meet environmental standards. Power is produced in a generator linked directly to the gas turbine. The gas turbine exhaust gases are sent to a heat recovery steam generator to produce superheated steam that can be used in a steam turbine to produce additional power. In this paper a comparative study between a 1000 MW combined cycle power plant and 1000 kW diesel power plant is presented. In first step, the energetic situation in Brazil, the needs of the electric sector modification and the needs of demand management and integrated means planning are clarified. In another step the characteristics of large and small thermoelectric power plants that use natural gas and diesel fuel, respectively, are presented. The ecological efficiency levels of each type of power plant is considered in the discussion, presenting the emissions of particulate material, sulphur dioxide (SO2), carbon dioxide (CO2) and nitrogen oxides (NOx). (c) 2006 Elsevier Ltd. All rights reserved.

Aplicação da parafina e do óleo de linhaça como hidrofobizantes da vermiculita, para remoção de derivados de óleo diesel resentes em água produzida sintética

Produced water has lately aroused interest due to their high degree of salinity, suspended oil particles, chemicals added in various manufacturing processes, heavy metals and radioactivity sometimes. Along with oil and due to its high volume production, water production is one of the pollutants of most concern in the process of oil extraction. PAHs due to their ubiquity and their characteristics carcinogenic or mutagenic and teratogenic even have attracted the attention of every scientific society. Formed from the incomplete combustion of organic matter may be natural or anthropogenic. Some materials have been researched with the goal of cleaning up environmental matrices that may be contaminated by hydrocarbons. Among these materials researched various clays have been employed, of which highlights the vermiculite. The family of phyllosilicates, vermiculite for its potential and its high hydrophobic surface area has been a tool widely used in the decontamination of water in processes of oil spills. However, when it loses its capacity expanded hydrophobic having the necessity of using a hidrofobizante to make it organophilic. Among the numerous hidrofobizantes researched and used the linseed oil was the pioneer. In this study sought to evaluate the capacity of removal of PAHs using the vermiculite hydrofobized with linseed oil and wax also, for it was made use of the 24 full factorial design as the main tool for the experiments. We also evaluated the clay grain size (-20 +48 and -48 +80 #), the percentage of hidrofobizante applied (5 and 10%) and salinity of the water produced synthesized in our laboratory (35,000 and 55,000 ppm). The molecular fluorescence spectroscopy due to its sensitivity and speed was used to verify the adsorption capacity of clay, as well as gas chromatography served as an auxiliary technique to identify and quantify the PAHs in solution. In order to characterize the vermiculite was made use of X-ray fluorescence and X-ray diffraction. The infrared and thermogravimetry were essential to note hydrophobization and the amount of coating of clay. According to the fluorescence analysis showed that the test 12 was the best result in about 98% adsorption of fluorescent compounds, however the high salinity, the smallest particle size, the highest percentage of hidrofobizante and the use of linseed oil showed greater efficiency in the removal capacity of these hydrocarbons, in accordance with the trend followed by the analysis of the major factors of the factorial design. To verify the adsorption capacity of clay using a fixed volume of water produced synthetically, used as the test base 12, at their respective levels and factors. Thus, it was observed that after adding about 1 ½ liters of water solution produced synthetically, about 300 times its volume in mass, the vermiculite was able to adsorb 80% of fluorescent species present in solution

Dessulfurizacao oxidativa em diesel utilizando catalisadores abase de vanádio ou manganês

Conselho Nacional de Desenvolvimento Científico e Tecnológico

Remediação de solos contaminados com diesel por lavagem com solução de tensoativos

Combating pollution of soils is a challenge that has concerned researchers from different areas and motivated the search for technologies that aim the recovery of degraded soils. Literature shows numerous processes that have been proposed with the intent of remediating soils contaminated by oils and other by-products of the oil industry, considering that the processes available have, generally, high operating costs, this work proposes a costeffective alternative to the treatment of Diesel-contaminated soils. The washing solutions were prepared using water as aqueous phase, the saponified coconut oil (OCS) as surfactant and n-butanol as co-surfactant. In this study, the soil was characterized by physical and chemical analyses. The study of diesel desorption from the soil was held in bath, using hexane and washing solutions, which had 10 and 20 wt.% active matter (AM - co-surfactant/surfactants) respectively. The study of the influence of active matter concentration and temperature in bath agitated used an experimental planning. The experiment also developed a system of percolation in bed to wash the soil and studied the influence of the concentration of active substance and volume of washing solution using an experimental planning. The optimal times to achieve hexane extraction were 30 and 180 min, while the best results using a 10% AM was 60 min and using a 20% AM was 120 min. The results of the experimental planning on bath showed that the maximum diesel removal was obtained when at a 20 wt.% of AM and under 50 °C, removing 99.92% of the oil. As for experiments in the system of percolation soil bed, the maximum diesel removal was high when the volume of the washing solution was of 5 L and the concentration of 20% AM. This experiment concluded that the concentration of AM and the temperature were vital to bath experiments for diesel removal, while in the system of percolation soil bed only concentration of AM influenced the soil remediation

Dessulfurização oxidativa em diesel utilizando catalisadores à base de vanádio ou manganês

The oxidative desulfurization process (ODS) of a commercial diesel fuel was performed under mild conditions in the presence of catalysts based on vanadium or manganese, supported on alumina, clays (commercial, natural and pillared) and zeolites (NaX, NaY, beta, mordenite and ZSM-5). The catalysts were synthesized by wet impregnation and characterized by X-ray diffraction, textural analysis by N2 adsorption and scanning electron microscopy. The dibenzothiophene (DBT) was used as sulfur compound in catalytic evaluation. The reactions were performed using acetonitrile as solvent and the hydrogen peroxide as oxidant at 55°C. The reaction products were analized by gas chromatography (GC-FID). In the studied conditions, the process was efficient due to the DBT was converted to its corresponding sulfone. Both DBT and corresponding sulfone were extracted by the solvent. Removals and oxidations up to 100% of sulfur compound were achieved. The catalysts supported on ZSM-5 zeolite showed are more effective for oxidation reaction of sulfur compound, presenting the best results. It was observed for oxidation reaction, that vanadium catalysts were more effective and manganese catalysts showed best results for removal of sulfur compounds

Obtenção de diesel verde por craqueamento termocatalítico de óleo de buriti (Mauritia flexuosa L.) sobre materiais nanoestruturados do tipo LaSBA-15

In order to obtain a biofuel similar to mineral diesel, lanthanum-incorporated SBA- 15 nanostructured materials, LaSBA-15(pH), with different Si/La molar ratios (75, 50, 25), were synthesized in a two-steps hydrothermal procedure, with pH-adjusting of the synthesis gel at 6, and were used like catalytic solids in the buriti oil thermal catalytic cracking. These solids were characterized by X-ray fluorescence (XRF), powder X-ray diffraction (XRD), thermogravimetric analysis (TG/DTG), infrared spectroscopy (FTIR), nitrogen porosimetry and ethanol dehydration, aiming to active sites identify. Taken together, the analyses indicated that the synthesis method has employed to obtain materials highly ordered mesostructures with large average pore sizes and high surface area, besides suggested that the lanthanum was incorporated in the SBA-15 both into the framework as well as within the mesopores. Catalytic dehydration of ethanol over the LaSBA-15(pH) products has shown that they have weak Lewis acid and basic functionalities, indicative of the presence of lanthanum oxide in these samples, especially on the La75SBA-15(pH) sample, which has presented the highest selectivity to ethylene. The buriti oil thermal and thermal catalytic cracking, realized from the room temperature to 450 ºC in a simple distillation system, has allowed obtaining two liquid fractions, each consisting of two phases, one aqueous and another organic, organic liquid (OL). The OL obtained from first fractions has shown high acid index, even in the thermal catalytic process. One the other hand, OL coming from second ones, called green diesel (GD), have presented low acid index, particularly that one obtained from the thermal catalytic process realized over LaSBA-15(pH) samples. The acid sites presence in these samples, associated to their large average pore sizes and high surface areas, have allowed them, especially the La75SBA-15(pH), to present deoxygenating activity in the buriti oil thermal catalytic cracking, providing an oxygenates content reduction, particularly carboxylic acids, in the GD. Furthermore, the GD comes from the second liquid fraction obtained in the buriti oil thermal catalytic cracking over this latest solid sample has shown hydrocarbons composition and physic-chemical properties similar to that mineral diesel, beyond sulfur content low

Genotoxicity assessment of water soluble fractions of biodiesel and its diesel blends using the Salmonella assay and the in vitro MicroFlow (R) kit (Litron) assay

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

Cytotoxicity of water-soluble fraction from biodiesel and its diesel blends to human cell lines

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

Biodegradability of commercial and weathered diesel oils

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

Use of weathered diesel oil as a low-cost raw material for biosurfactant production

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

The use of vinasse as an amendment to ex-situ bioremediation of soil and groundwater contaminated with diesel oil

Este trabalho investigou a possibilidade de se usar a vinhaça como um agente estimulador de processos de biorremediação ex-situ. Amostras de água subterrânea e solo foram coletadas em três postos de combustíveis. A biorremediação do solo foi simulada em frascos de Bartha, usados para medir a produção de CO2, durante 48 dias, onde a vinhaça foi adicionada a uma concentração de 33 mL.Kg-1 de solo. A eficiência de biodegradação também foi medida pela quantificação de hidrocarbonetos totais de petróleo (TPH) por cromatografia gasosa. A biorremediação da água subterrânea foi realizada em experimentos laboratoriais simulando condições aeradas (bioreatores) e não aeradas (frascos de DBO). em ambos os casos, a concentração de vinhaça foi de 5 % (v/v) e diferentes parâmetros físico-químicos foram avaliados durante 20 dias. Embora um aumento da fertilização e da população microbiana do solo foram obtidos com a vinhaça, esta estratégia não se mostrou adequada em aumentar a eficiência da biorremediação dos solos contaminados com óleo diesel. A adição de vinhaça às águas subterrâneas contaminadas teve efeitos negativos na biodegradação dos hidrocarbonetos, uma vez que a vinhaça, como uma fonte de carbono facilmente assimilável, foi preferencialmente consumida.

Investigation about the efficiency of the bioaugmentation technique when applied to diesel oil contaminated soils

Este trabalho investigou a eficiência da técnica do bioaumento quando aplicada a solos contaminados com óleo diesel coletados em três postos de combustíveis. Experimentos de biodegradação foram realizados em frascos de Bartha (250 mL), usados para medir a produção microbiana de CO2. A eficiência de biodegradação também foi quantificada pela concentração de hidrocarbonetos. Conjuntamente aos experimentos de biodegradação, a capacidade das culturas estudadas e dos microrganismos nativos em biodegradar óleo diesel comprado de um posto de combustíveis local, foi verificada utilizando-se a técnica baseada no indicador redox 2,6 - diclorofenol indofenol (DCPIP). Resultados obtidos com esse teste mostraram que os inóculos empregados nos experimentos de biodegradação foram capazes de biodegradar óleo diesel e os testes com os microrganismos nativos indicaram que estes solos previamente apresentavam uma microbiota adaptada para degradar hidrocarbonetos. em suma, nenhum ganho foi obtido com a adição dos microrganismos ou mesmo efeitos negativos foram observados nos experimentos de biodegradação.

Biodegradation of biodiesel/diesel blends by Candida viswanathii

This work is aimed to assess the aerobic biodegradation of biodiesel/diesel blends (0, 2, 5, 20 and 100%, v/v) by Candida viswanathii. The biodegradation potential of the inoculum was assessed with the redox indicator 2,6-dichlorophenol indophenol (DCPIP) test and with respirometric experiment in biometer flasks (250 mL) used to measure the microbial CO(2) production. In the latter, the inoculum was added to a contaminated soil with the blends (addition of 50 mL of fuel/Kg of soil from a non-contaminated site). C. viswanathii was able to increase significantly (approximately 50% in terms of CO(2) production) the biodegradation in soil of biodiesel/diesel blends and neat biodiesel since it preferable biodegrades biodiesel. Without inoculum the biodegradation of diesel oil was higher than biodiesel and blends (47.3, 51.1, 5.7 and 22.1% in terms of CO(2) production by B2, B5, B20 and B100, respectively) presumably due to the presence of the antioxidant terc-butyl-hydroquinone (TBHQ) in the biodiesel.

Aerobic biodegradation of butanol and diesel oil blends

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