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

Matrizes poliméricas puras e modificadas para adsorção do gás sulfeto de hidrogênio

The underground natural gas found associated or not with oil is characterized by a mixture of hydrocarbons and residual components such as carbon dioxide (CO2), nitrogen gas (N2) and hydrogen sulfide (H2S), called contaminants. The H2S especially promotes itself as a contaminant of natural gas to be associated with corrosion of pipelines, to human toxicity and final applications of Natural Gas (NG). The sulfur present in the GN must be fully or partially removed in order to meet the market specifications, security, transport or further processing. There are distinct and varied methods of desulfurization of natural gas processing units used in Natural Gas (UPGN). In order to solve these problems have for example the caustic washing, absorption, the use of membranes and adsorption processes is costly and great expenditure of energy. Arises on such findings, the need for research to active processes of economic feasibility and efficiency. This work promoted the study of the adsorption of sulfide gas in polymer matrices hydrogen pure and modified. The substrates of Poly(vinyl chloride) (PVC), poly(methyl methacrylate) (PMMA) and sodium alginate (NaALG) were coated with vanadyl phosphate compounds (VOPO4.2H2O), vanadium pentoxide (V2O5), rhodamine B (C28H31N2O3Cl) and ions Co2+ and Cu2+, aiming to the adsorption of hydrogen sulfide gas (H2S). The adsorption tests were through a continuous flow of H2S in a column system (fixed bed reactor) adsorption on a laboratory scale. The techniques used to characterize the adsorbents were Infrared spectroscopy (FTIR), thermogravimetry analysis (TGA), X-ray fluorescence (XRF), the X-ray diffraction (XRD) electron microscopy (SEM). Such work indicates, the results obtained, the adsorbents modified PMMA, PVC and NaALG have a significant adsorptive capacity. The matrix that stood out and had the best adsorption capacity, was to ALG modified Co2+ with a score of 12.79 mg H2S / g matrix

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

Tratamento de borra de petróleo com sistemas microemulsionados

During the storage of oil, sludge is formed in the bottoms of tanks, due to decantation, since the sludge is composed of a large quantity of oil (heavy petroleum fractions), water and solids. The oil sludge is a complex viscous mixture which is considered as a hazardous waste. It is then necessary to develop methods and technologies that optimize the cleaning process, oil extraction and applications in industry. Therefore, this study aimed to determine the composition of the oil sludge, to obtain and characterize microemulsion systems (MES), and to study their applications in the treatment of sludge. In this context, the Soxhlet extraction of crude oil sludge and aged sludge was carried out, and allowing to quantify the oil (43.9 % and 84.7 % - 13 ºAPI), water (38.7 % and 9.15 %) and solid (17.3 % and 6.15 %) contents, respectively. The residues were characterized using the techniques of X-ray fluorescence (XRF), Xray diffraction (XRD) and transmission Infrared (FT-IR). The XRF technique determined the presence of iron and sulfur in higher proportions, confirming by XRD the presence of the following minerals: Pyrite (FeS2), Pyrrhotite (FeS) and Magnetite (Fe3O4). The FT-IR showed the presence of heavy oil fractions. In parallel, twelve MES were prepared, combining the following constituents: two nonionic surfactants (Unitol L90 and Renex 110 - S), three cosurfactants (butanol, sec-butanol and isoamyl alcohol - C), three aqueous phase (tap water - ADT, acidic solution 6 % HCl, and saline solution - 3.5 % NaCl - AP) and an oil phase (kerosene - OP). From the obtained systems, a common point was chosen belonging to the microemulsion region (25 % [C+S] 5 % OP and AP 70 %), which was characterized at room temperature (25°C) by viscosity (Haake Rheometer Mars), particle diameter (Zeta Plus) and thermal stability. Mixtures with this composition were applied to oil sludge solubilization under agitation at a ratio of 1:4, by varying time and temperature. The efficiencies of solubilization were obtained excluding the solids, which ranged between 73.5 % and 95 %. Thus, two particular systems were selected for use in storage tanks, with efficiencies of oil sludge solubilization over 90 %, which proved the effectiveness of the MES. The factorial design delimited within the domain showed how the MES constituents affect the solubilization of aged oil sludge, as predictive models. The MES A was chosen as the best system, which solubilized a high amount of aged crude oil sludge (~ 151.7 g / L per MES)

Estudo da influência do biodiesel de mamona como aditivo antioxidante para o biodiesel de girassol e soja

Biodiesel is a fuel made up by mono-alkyl-esters of long chain fatty acids, derived from vegetable oils or animal fat. This fuel can be used in compression ignition engines for automotive propulsion or energy generation, as a partial or total substitute of fossil diesel fuel. Biodiesel can be processed from different mechanisms. Transesterification is the most common process for obtaining biodiesel, in which an ester compound reacts with an alcohol to form a new ester and a new alcohol. These reactions are normally catalyzed by the addition of an acid or a base. Initially sunflower, castor and soybean oil physicochemical properties are determined according to standard test methods, to evaluate if they had favorable conditions for use as raw material in the transesterification reaction. Sunflower, castor and soybean biodiesel were obtained by the methylic transesterification route in the presence of KOH and presented a yield above 93% m/m. The sunflower/castor and soybean/castor blends were studied with the aim of evaluating the thermal and oxidative stability of the biofuels. The biodiesel and blends were characterized by acid value, iodine value, density, flash point, sulfur content, and content of methanol and esters by gas chromatography (GC). Also studies of thermal and oxidative stability by Thermogravimetry (TG), Differential Scanning Calorimetry High Pressure (P-DSC) and dynamic method exothermic and Rancimat were carried out. Biodiesel sunflower and soybean are presented according to the specifications established by the Resolution ANP no 7/2008. Biodiesel from castor oil, as expected, showed a high density and kinematic viscosity. For the blends studied, the concentration of castor biodiesel to increased the density, kinematic viscosity and flash point. The addition of castor biodiesel as antioxidant in sunflower and soybean biodiesels is promising, for a significant improvement in resistance to autoxidation and therefore on its oxidative stability. The blends showed that compliance with the requirements of the ANP have been included in the range of 20-40%. This form may be used as a partial substitute of fossil diesel

Adsorção dos gases NH3, NO e H2S em fosfato de vanadila, hidrogeno fosfato de vanadila e fosfatos de vanadila dopados por Al, Co, Mn e Cr

In this work were synthesized the materials called vanadyl phosphate, hydrogen vanadyl phosphate and vanadyl phosphate doped by transition metals with the aim in adsorption the following compounds: ammonia, hydrogen sulfide and nitrogen oxide. To characterize the starting compounds was used DRX, FTIR, FRX and TG analysis. After the characterization of substrates, proceeded de adsorption of NH3 and H2S gases in reactor, passing the gases with continuous flow for 30 min and room temperature. Gravimetric data indicate that the matrices of higher performance in adsorption of ammonia was those doped by aluminum and manganese, obtaining results of 216,77 mgNH3/g and 200,40 mgNH3/g of matrix, respectively. The matrice of higher performance in adsorption of hydrogen sulfide was that doped by manganese, obtaining results of 86,94 mgH2S/g of matrix. The synthesis of substrates VOPO4.2H2O and MnVOPO4.2H2O with nitrogen oxide was made in solution, aiming the final products VOPO4.G.nH2O and MnVOPO4.G.nH2O (G = NO and n = number of water molecules). The thermo analytical behavior and the infrared spectroscopy are indicative of formation of VOPO4.2,5NO.3H2O compound. Results of scanning electron microscopy (SEM) and Energy dispersive spectroscopy (EDS) of materials vanadyl phosphate and vanadyl phosphate modified after reaction in solid state or in solution with the gases show morphology changes in substrates, beyond the formation of orthorhombic sulfur crystals over their respective hosts when these adsorb hydrogen sulfide

Efeito da aplicação foliar de boro e zinco sobre a produção e os teores de SST e ATT dos frutos da Pereira-Japonesa e da pinheira

Pulverizações foliares com produtos contendo micronutrientes, dentre os quais os produtos quelatizados, são utilizadas com relativa freqüência em frutíferas, sem o embasamento científico adequado, principalmente entre os agricultores mais tecnificados. Neste contexto, o objetivo deste trabalho foi verificar o efeito da aplicação via foliar de B e Zn sobre a produção e os teores de SST e ATT dos frutos da Pereira-Japonesa e da Pinheira. O experimento foi conduzido numa área irrigada, situada no cinturão verde do município de Ilha Solteira-SP. O solo da área foi classificado como Podzólico Vermelho-Escuro. Foram utilizadas plantas de Pereira-Japonesa, cultivar Okussankichi e de Pinheira. Os tratamentos utilizados foram: T1. apenas água; T2. ácido bórico; T3. sulfato de zinco; T4. T2 + T3; T5. ácido bórico + uréia + ácido cítrico + EDTA; T6. sulfato de zinco + uréia + ácido cítrico + EDTA; T7. T5 + T6; T8. ácido bórico + uréia + ácido cítrico + EDTA + molibdato de sódio + enxofre + cloreto de cálcio; T9. sulfato de zinco + ácido cítrico + EDTA + sulfato de Fe + sulfato de Mn + sulfato de Mg, e T10. T8+T9. Foram utilizadas doses de 110 g ha-1 de B e 250 g ha-1 de Zn, em cada aplicação. O delineamento experimental adotado foi o de blocos ao acaso, com quatro repetições e, para comparação de médias, foi utilizado o teste de Tukey. Com base nos resultados obtidos, pode-se concluir que: 1) a produção e os teores de SST e ATT dos frutos da pereira-japonesa e da pinheira não foram influenciados pela aplicação foliar de B e de Zn; b) a mistura de ácido bórico com quelatos foi eficiente no fornecimento de B às plantas de pereira- japonesa, o mesmo não ocorrendo para pinheira, c) o sulfato de zinco + produtos quelatizantes foram eficientes no aumento dos teores foliares de Zn somente na pereira.

Composição química e nutrientes em sementes das espécies florestais Pente de Macaco, Flor de Paca, Itaúba, Jatobá e Murici Manso

A considerable number of tree species is the flora in some cases, their fruits and seeds turn out to be good sources of nutrientes. The study aimed to verify the chemical composition of nutrientes in seeds of forest species Pente de Macaco, Flor de Paca, Ita ba, Jatoba and Murici Manso. of forest species of Monkey Comb, Flor de Paca, Ita ba, Jatoba and Murici Manso. The experimental design was randomized with five treatments. Analyses were carried out: moisture content, starch content (mg. g (1)), carbohydrates (mg. g (1)), and proteins (albumin, globulin, prolamin, glutelin) (mg. g (1)) and nutrients (N, P, K, Ca, Mg and S). The results showed that the seeds of Flor de Paca had the highest content of starch and protein of Jatoba is a significant source of carbohydrates and the highest levels of phosphorus, calcium and sulfur. For contents of nitrogen Ita ba showed the highest levels and also obtained satisfactory results for calcium and species Murici Manso had the highest levels of potassium and magnesium.

Monitoramento da qualidade das ásguas de chuvas conforme a atuação dos sistemas sinóticos na cidade de Natal/RN

Acid rain is a major assault on the environment, a consequence of burning fossil fuels and industrial pollutants the basis of sulfur dioxide released into the atmosphere. The objective of this research was to monitor and analyze changes in water quality of rain in the city of Natal, seeking to investigate the influence of quality on a local, regional and global, in addition to possible effects of this quality in the local landscape. Data collection was performed from December 2005 to December 2007. We used techniques of nefanálise in identifying systems sinóticos, field research in the search for possible effects of acid rain on the landscape, and collect and analyze data of precipitation and its degree of acidity. Used descriptive statistics (standard deviation and coefficient of variation) used to monitor the behavior of chemical precipitation, and monitoring of errors in measurements of pH, level of confidence, Normalized distribution of Gauss, confidence intervals, analysis of variance ANOVA were also used. Main results presented as a variation of pH between 5,021 and 6,836, with an average standard deviation of 5,958 and 0,402, showing that the average may represent the sample. Thus, we can infer that, according to the CONAMA Resolution 357 (the index for fresh water acidity should be between 6.0 and 9.0), the precipitation of Natal / RN is slightly acidic. It appears that the intertropical convergence zone figures showed the most acidic among the systems analyzed sinóticos, taking its average value of pH of 5,617, which means an acid value now, with a standard deviation of 0,235 and the coefficient of variation of 4,183% which shows that the average may represent the sample. Already in field research and found several places that suffer strongly the action of acid rain. However, the results are original and need further investigation, including the use of new methodologies

Clivagem dos ciclopaladados diméricos [Pd(dmba)(m-X)]2 (dmba = N,N-dimetilbenzilamina; X = Cl, N3, NCO) por tiouréia

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Novos processos de reciclagem de chumbo

O processo pirometalúrgico convencional para a produção de chumbo metálico é comparado com dois novos processos ambientalmente não agressivos: o eletrohidrometalúrgico e fusão alcalina. O processo eletrohidrometalúrgico consiste em reduzir o tamanho das partículas dos compostos de chumbo e lixiviar os mesmos com uma solução ácida de fluoborato férrico. Neste ponto, o chumbo é dissolvido com os íons férricos sendo reduzidos a íons ferrosos. A solução resultante da lixiviação é bombeada para os compartimentos catódicos de uma célula eletrolítica de diafragma nos quais o chumbo metálico é depositado em catodos de aço inoxidável numa forma compacta e pura. A solução que é empobrecida em íons Pb2+ é então enviada aos compartimentos anódicos da mesma célula onde, nas superfícies de anodos ocorre a oxidação dos íons ferrosos a férricos, que retornam ao estágio de lixiviação. O processo de fusão alcalina consiste em se juntar soda cáustica fundida, enxofre e compostos de chumbo num reator a uma temperatura entre 600 °C e 700 °C. Como um resultado chumbo metálico é obtido juntamente com sais fundidos de sódio, sulfetos metálicos e borra. O fundido é processado, resultando em borra, sulfetos metálicos, soda cáustica e enxofre. Estes dois últimos retornam para o reator. Ambos os processos permitem a recuperação de metais como antimônio, estanho, enxofre e prata, que em processo convencional são perdidos na escória. Esses novos processos são ambientalmente corretos sem poluições severas de Pb e SO2. O chumbo metálico obtido é mais puro que aquele do processo convencional.

Atmospheric pollution effects on childhood health: an environmental study in the Paraíba Valley

OBJETIVOS: estimar as correlações entre os níveis de poluentes atmosféricos e o número de internações por doença respiratória em crianças, em hospital universitário. MÉTODOS: trata-se de um estudo ecológico de série temporal. Os dados sobre poluentes atmosféricos foram obtidos junto à CETESB e os dados sobre internação hospitalar, junto ao SAME do Hospital Universitário de Taubaté, Brasil. O estudo se refere a dados e internação do ano de 2001. Para estudar as correlações dos valores dos poluentes entre si e entre as internações, utilizou-se da técnica de correlação de Pearson. Foram estimados os riscos relativos para internação por doença respiratória comparando os quartis dos agentes poluentes com os valores do primeiro quartil. A significância estatística adotada foi alfa = 5%. RESULTADOS: foram internadas 158 crianças com doença respiratória no ano de 2001 (30% do total de internações no ano). Os poluentes estiveram correlacionados entre si e houve correlação positiva, entre o número de internação e dióxido de enxofre e material particulado; houve aumento de 25% no risco de internação comparando o quarto quartil e o primeiro quartil. CONCLUSÕES: houve correlação positiva entre número de internações por doenças respiratórias e poluentes atmosféricos.

Nutrição mineral do mamoeiro (Carica papaya L.): III - sintomatologia de carências nutricionais

Objetivando caracterizar as deficiências de N, P, K, Ca, Mg e S em mamoeiro (Carica papaya L.) em condições de casa de vegetação e soluções nutritivas, desenvolveu-se o presente trabalho. Os autores descrevem os sintomas de carência dos macronutrientes, com exceção do enxofre, cujas plantas que receberam o tratamento deficiente neste nutriente, não mostraram sintomas, provavelmente por contaminação externa. Os níveis analíticos encontrados em folhas sadias e desnutridas, expressos em função da matéria seca foram: N-4,24% e 3,61%; P-0,52% e 0,14%; K-3,81% e 1,36%; Ca-1,29% e 0,28%; Mg-0,65 e 0,17%.

Multivariate analysis of stable isotope data in the traceability process for birds

A análise isotópica tem se mostrado uma ferramenta de suma importância ao processo de rastreabilidade, no entanto, existem divergências nas análises estatísticas dos resultados, uma vez que os dados são dependentes e advindos de vários elementos químicos tais como Carbono, Hidrogênio, Oxigênio, Nitrogênio e Enxofre (CHON'S). Com o intuito de estabelecer a análise propícia para os dados de rastreabilidade em aves pela técnica de isótopos estáveis e avaliar a necessidade da análise conjunta das variáveis, foram usados dados de carbono-13 e de nitrogênio-15 de ovos (albúmen + gema) de poedeiras e músculo peitoral de frangos de corte, os quais foram submetidos à análise estatística univariada (Anova e complementada pelo teste de Tukey) e multivariada (Manova e Discriminante). Os dados foram analisados no software Minitab 16, e os resultados, consolidados na teoria, confirmam a necessidade de análise multivariada, mostrando também que a análise discriminante esclarece as dúvidas apresentadas nos resultados de outros métodos de análise comparados nesta pesquisa.

Nutrição e produtividade de híbridos de sorgo granífero de ciclos contrastantes consorciados com capim-marandu

O objetivo deste trabalho foi avaliar o efeito do consórcio com capim-marandu (Urochloa brizantha) na nutrição e produtividade de híbridos de sorgo granífero de ciclos contrastantes, em sistema plantio direto. Utilizou-se o delineamento experimental de blocos ao acaso, em arranjo fatorial 2x2, com seis repetições. Os tratamentos consistiram de dois híbridos de sorgo granífero de ciclos contrastantes (P8118, ciclo médio; e P8419, ciclo precoce) e dois sistemas de cultivo (monocultivo e consórcio com capim-marandu na linha de semeadura), com semeadura no início de dezembro. Avaliou-se a nutrição, as características agronômicas, os componentes da produção e a produtividade de matéria seca e grãos da cultura do sorgo. Com exceção do potássio e do enxofre, os teores foliares dos demais nutrientes foram adequados à cultura do sorgo granífero, em todos os tratamentos. O híbrido P8118 apresentou a maior produtividade de grãos e, após o consórcio, contribuiu para a maior produtividade de matéria seca da forragem de capim-marandu, no corte realizado em outubro. O cultivo consorciado com capim-marandu não afeta a nutrição e a produtividade de matéria seca e de grãos de sorgo, em comparação ao monocultivo, independentemente do ciclo do híbrido utilizado.