Aplicação de sabões de ácidos graxos epoxidados como inibidores de corrosão em oleoduto

Corrosion usually occurs in pipelines, so that it is necessary to develop new surface treatments to control it. Surfactants have played an outstanding role in this field due to its capacity of adsorbing on metal surfaces, resulting in interfaces with structures that protect the metal at low surfactant concentrations. The appearance of new surfactants is a contribution to the area, as they increase the possibility of corrosion control at specific conditions that a particular oil field presents. The aim of this work is to synthesize the surfactants sodium 12 hydroxyocadecenoate (SAR), sodium 9,10-epoxy-12 hydroxyocadecanoate (SEAR), and sodium 9,10:12,13-diepoxy-octadecanoate (SEAL) and apply them as corrosion inhibitors, studying their action in environments with different salinities and at different temperatures. The conditions used in this work were chosen in order to reproduce oil field reality. The study of the micellization of these surfactants in the liquid-gas interface was carried out using surface tensiometry. It was observed that cmc increased as salt concentration was increased, and temperature and pH were decreased, while cmc decreased with the addition of two epoxy groups in the molecule. Using the values of cmc and the Gibbs equation, the values of Gibbs free energy of adsorption, area per adsorbed molecule, and surface excess were calculated. The surface excess increases as salt concentration and temperature decreases, increasing as pH is increased. The area per adsorbed molecule and the free energy of adsorption decrease with salt concentration, temperature, and pH increase. SAXS results showed that the addition of epoxy group in surfactant structure results in a decrease in the repulsion between the micelles, favoring the formation of more oblong micellar structures, ensuring a better efficiency of metal coverage. The increase in salt and surfactant concentrations provides an increase in micellar diameter. It was shown that the increase in temperature does not influence micellar structure, indicating thermal stability that is advantageous for use as corrosion inhibitor. The results of inhibition efficiency for the surfactants SEAR and SEAL were considered the best ones. Above cmc, adsorption occurred by the migration of micelles from the bulk of the solution to the metal surface, while at concentrations below cmc film formation must be due to the adsorption of semi-micellar and monomeric structures, certainly due to the presence of the epoxy group, which allows side interactions of the molecule with the metal surface. The metal resistance to corrosion presented values of 90% of efficiency. The application of Langmuir and Frumkin isotherms showed that the later gives a better description of adsorption because the model takes into account side interactions from the adsorbing molecules. Wettability results showed that micelle formation on the solid surface occurs at concentrations in the magnitude of 10-3 M, which isthe value found in the cmc study. This value also justifies the maximum efficiencies obtained for the measurements of corrosion resistance at this concentration. The values of contact angle as a function of time suggest that adsorption increases with time, due to the formation of micellar structures on metal surface

Síntese, caracterizaçao e propriedades catalicas da peneira molecular nanoestruturada modificada com lantanio

The nanostructured molecular sieve SBA-15 was synthesized by the hydrothermal method, and modified with lanthanum with Si/La molar ratios of 25, 50, 75 and 100. The materials were evaluated as catalysts for the cracking of n-hexane model reaction. Type SBA- 15 and LaSBA-15 mesoporous materials were synthesized using tetraetilortosilicato as a source of silica, hydrochloric acid, heptahydrate lanthanum chloride and distilled water. Pluronic P123 triblock. polymer was used as structure template. The syntheses were carried out by 72 hours. The obtained SBA-15 samples were previously analyzed by thermogravimetry, in order to check the conditions of calcination for removal of organic template. Then, the calcined materials were characterized by X-ray diffraction, infrared spectroscopy, adsorption and desorption of nitrogen, scanning electron microscopy and X-ray microanalysis by dispersive energy. The acidity of the samples was determined using adsorption of n-bulinamina and desorption followed by thermogravimetry. It was found that the hydrothermal synthesis method was suitable for the synthesis of the SBA-15 mesoporous materials, with an excellent degree of hexagonal ordering. The reactions of catalytic cracking of n-hexane were carried out using a fixed bed continuous flow microreactor, coupled on-line to a gas chromatograph. From the catalytic evaluation, it was observed that the mesoporous materials containing lanthanum showed different results for the reaction of cracking of nhexane compared to the unmodified mesoporous material SBA-15. As a result of cracking was obtained as main products hydrocarbons in the range of C1 to C5. The catalyst that showed better properties in relation to the acidity and catalytic activity was LaSBA-15 with the ratio Si/La = 50

Avaliação oxidativa do biodiesel de pinhão manso em diferentes processos de purificação

The objective of this study was to analyze the oxidative stability of biodiesel from jatropha obtained from different purification processes, three wet processes with different drying (in a vacuum oven, conventional oven and in anhydrous sodium sulfate) and dry (purification with magnesium silicate adsorbent). Raw materials of different qualities (jatropha crop ancient and recent crop) were used. The Jatropha oil was extracted by mechanical extraction and refined. The Jatropha biodiesel was obtained by the transesterification reaction in ethyl route using alkaline catalysis. The biodiesel samples were characterized by analysis of water content, carbon residue, Absorption Spectroscopy in the Infrared Region and Thermogravimetry. Thermogravimetric curves of purified PUsv* PUsq* and had higher initial decomposition temperatures, indicating that the most stable, followed by samples PU* and PUSC*. Besides the sample SP* is a smaller initial temperature, confirming the sample without purification to be less thermally stable. The percentage mass loss of the purified samples showed conversion of about 98.5%. The results of analyzes carbon residue and infrared suggested that contamination by impurities is the main factor for decreased oxidative stability of biodiesel. The oxidative stability was assessed from periodic monitoring, using the techniques of Rancimat, peroxide index, acid value and Pressurized Differential Scanning Calorimetry. Samples of biodiesel from jatropha which showed better oxidative stability were of the best quality raw material and wet scrubbing: PUsq* with dry chemical, using anhydrous sodium sulfate and PUsv* with vacuum drying, which had oxidative stability 6 hours in Rancimat time 0 days, within the limits established by the Technical Regulation No. 4/2012 of the ANP, without the addition of antioxidant, suggesting that these procedures the least influence on the oxidative stability of biodiesel

Craqueamento térmico e termocatalítico do óleo de girassol (Hellianthus annus L.) sobre materiais micro e mesoporosos

Microporous materials zeolite type Beta and mesoporous type MCM-41 and AlMCM-41 were synthesized hydrothermally and characterized by methods of X-ray diffraction, Fourier transform infrared, scanning electron microscopy, surface acidity, nitrogen adsorption, thermal analysis TG / DTG. Also we performed a kinetic study of sunflower oil on micro and mesoporous catalysts. The microporous material zeolite beta showed a lower crystallinity due to the existence of smaller crystals and a larger number of structural defects. As for the mesoporous materials MCM-41 and AlMCM-41 samples showed formation of hexagonal one-dimensional structure. The study of kinetic behavior of sunflower oil with zeolite beta catalysts, AlMCM-41 and MCM-41 showed a lower activation energy in front of the energy of pure sunflower oil, mainly zeolite beta. In the thermal cracking and thermocatalytic of sunflower oil were obtained two liquid fractions containing an aqueous phase and another organic - organic liquid fraction (FLO). The FLO first collected in both the thermal cracking as the thermocatalytic, showed very high level of acidity, performed characterizations of physicochemical properties of the second fraction in accordance with the specifications of the ANP. The second FLO thermocatalytic collected in cracking of sunflower oil presented results in the range of diesel oil, introducing himself as a promising alternative for use as biofuel liquid similar to diesel, either instead or mixed with it

Estudo comparativo entre a pirólise do polietileno de baixa densidade, utilizando vermiculita modificada e SBA-15

Catalytic processes are widely present in everyday life. This results in large number of studies seeking materials that may combine the low cost catalytic efficiency. Based on this assumption, the clays have long been used as catalysts, with its huge availability, diversity and possibility of improving their properties from structural changes, primarily responsible for this great use. Among the natural clays, vermiculite due to their characteristic properties (high cation exchange capacity and expansion), is suitable for various applications including as catalysts and catalyst supports. In this work, the acid leaching of clay vermiculite was performed, coming from Santa Luzia-PB, with nitric acid (2, 3 and 4 mol / L) and subsequent calcination of the materials obtained. The materials were named as Vx/400, where x is the acid concentration employed and 400 used in calcination temperature. The effectiveness of changes made was determined by XRD techniques, FT-IR, EDS, TG/DTG, nitrogen physisorption and DTP of n-butylamine. Acid leaching has improved some properties of the clay - specific area and acidity - but the control of the acid concentration used is of vital importance, since the highest concentration caused the partial destruction of vermiculite entailing a decline in their properties. For analysis of the catalytic activity of the modified clay was made a comparative study with the SBA -15 mesoporous materials, synthesized via hydrothermal method, using the pyrolysis of low density polyethylene (LDPE). The results showed that the acid plays a fundamental role in the conversion of the polymer into smaller molecules, the material V3/400 was more selective for the source monomer (ethylene) due to their increased acidity, which promotes more breaks bonds in the polymeric chain, while materials and V0/400 V2/400, lower acidity, showed higher selectivity to light hydrocarbons, the range of fuel (41.96 and 41.23%, respectively), due to less breakage and secondary condensation reactions chains; already V4/400 SBA-15/550 and resulted in lower percentages of light hydrocarbons and the partial destruction of the structure and low acidity, respectively, responsible for the inefficiency of materials

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

Recuperação de um solo degradado com a aplicação de adubos verdes e lodo de esgoto

A utilização incorreta dos solos vem causando alterações neles, tornando-os cada vez menos produtivos, aumentando as áreas com solos degradados. O presente trabalho teve por objetivos estudar ações para acelerar a formação do horizonte A de um Latossolo Vermelho degradado, via uso de adubos verdes, lodo de esgoto e cultivo de uma espécie arbórea nativa de Cerrado, e selecionar indicadores para detectar alterações da camada superficial do solo. O monitoramento das alterações do solo foi realizado anualmente. O delineamento experimental foi o de blocos casualizados com seis tratamentos, em cinco repetições. Os tratamentos foram: testemunha - solo exposto (sem manejo); vegetação nativa (Cerrado); espécie arbórea Astronium fraxinifolium; Astronium fraxinifolium + Canavalia ensiformis; Astronium fraxinifolium + Raphanus sativus; e Astronium fraxinifolium + Brachiaria decumbens + lodo de esgoto (60 t ha-1). Avaliou-se no solo: porosidade, densidade do solo, cátions trocáveis, pH, acidez potencial (H + Al), soma de bases (SB), saturação por bases (V), CTC e macrorganismos. Nos adubos verdes, foi avaliada a massa seca e, para a espécie arbórea, a altura e o diâmetro de caule. A mobilização do solo e a mobilização mais a adubação verde e o lodo de esgoto estão recuperando as propriedades do solo degradado, com comportamento semelhante entre elas após um ano de adoção. O melhor indicador físico das alterações do solo foi sua densidade. Os tratamentos adotados são semelhantes quanto à população de macrorganismos do solo e contribuindo positivamente para recuperação da macrofauna. A presença de larva e besouro foi indicadora da melhoria da macrofauna do solo.

Influence of organic-mineral fertilization of an oxisol on soil chemical properties and Bracharia brizantha production

A utilização de fertilizante organomineral da indústria produtora dos aminoácidos lisina e treonina pode melhorar a fertilidade de solos tropicais. O presente trabalho teve como objetivo avaliar a influência de diferentes dosagens do fertilizante organomineral denominado Ajifer L-14 nos atributos químicos e no aumento de produção de forragem de um Latossolo Vermelho do noroeste paulista. O delineamento utilizado foi em blocos casualizados, com sete tratamentos e quatro repetições. Os tratamentos foram: T1- testemunha (sem aplicação de Ajifer L-14); T2- testemunha com vegetação natural; T3- adubação mineral de acordo com a necessidade da cultura e a análise do solo (usando 1,35 kg de ureia, 2,20 kg de superfosfato simples e 0,51 kg de KCl por parcela, o que corresponde a 60 kg de N, 40 kg de P2O5 e 30 kg ha-1 de K2O, respectivamente); T4- adubação com Ajifer L-14 de acordo com a recomendação da análise química do solo (40 L parcela-1, o que corresponde a 60 kg ha-1 N); T5- adubação com Ajifer L-14 em dosagem 50 % acima da recomendação (60 L parcela-1, o que corresponde a 90 kg ha-1 N; T6- adubação com Ajifer L-14 em dosagem 50 % abaixo da recomendação (20 L parcela-1, o que corresponde a 30 kg ha-1 N); T7- adubação com Ajifer L-14 em dosagem 25 % acima da recomendação (50 L parcela-1, o que corresponde a 75 kg ha-1 N); e T8- adubação com Ajifer L-14 em dosagem 25 % abaixo da recomendação (30 L parcela-1, o que corresponde a 45 kg ha-1 N). Nas profundidades de 0,0-0,1 e 0,1-0,2 m, avaliaram-se os seguintes atributos químicos do solo:, teor de matéria orgânica (MO), pH, K+, Ca2+, Mg2+, capacidade de troca catiônica (CTC), acidez potencial e saturação por bases. A aplicação do fertilizante organomineral não influenciou os atributos químicos do solo. Na análise de regressão, houve relação polinomial entre as doses de aplicação do fertilizante organomineral e a produção de massa seca e proteína bruta de Bracharia brizantha.

Estudo cinético da degradação térmica e catalítica de petróleo pesado usando Al-MCM-41

The mesoporous nanostructured materials have been studied for application in the oil industry, in particular Al-MCM-41, due to the surface area around 800 to 1.000 m2 g-1 and, pore diameters ranging from 2 to 10 nm, suitable for catalysis to large molecules such as heavy oil. The MCM-41 has been synthesized by hydrothermal method, on which aluminum was added, in the ratio Si/Al equal to 50, to increase the generation of active acid sites in the nanotubes. The catalyst was characterized by X-ray diffraction (XRD), surface area by the BET method and, the average pore volume BJH method using the N2 adsorption, absorption spectroscopy in the infrared Fourier Transform (FT-IR) and determination of surface acidity with application of a probe molecule - n-butylamine. The catalyst showed well-defined structural properties and consistent with the literature. The overall objective was to test the Al-MCM-41 as catalyst and thermogravimetric perform tests, using two samples of heavy oil with API º equal to 14.0 and 18.5. Assays were performed using a temperature range of 30-900 ° C and heating ratios (β) ranging from 5, 10 and 20 °C min-1.The aim was to verify the thermogravimetric profiles of these oils when subjected to the action of the catalyst Al- MCM-41. Therefore, the percentage ranged catalyst applied 1, 3, 5, 10 and 20 wt%, and from the TG data were applied two different kinetic models: Ozawa-Flynn-Wall (OFW) and Kissinger-Akahrira-Sunose (KAS).The apparent activation energies found for both models had similar values and were lower for the second event of mass loss known as cracking zone, indicating a more effective performance of Al-MCM-41 in that area. Furthermore, there was a more pronounced reduction in the value of activation energy for between 10 and 20% by weight of the oil-catalyst mixture. It was concluded that the Al-MCM-41 catalyst has applicability in heavy oils to reduce the apparent activation energy of a catalyst-oil system, and the best result with 20% by weight of Al-MCM-41

Reatividade de uma escória de siderurgia em um latossolo vermelho distrófico

O presente trabalho objetivou estudar a reatividade de uma escória de siderurgia de aciaria, em diferentes frações granulométricas, aplicada em uma amostra de um Latossolo Vermelho distrófico, ácido, em condições de laboratório. Utilizou-se um fatorial 4 x 3 + 2 com quatro repetições, sendo quatro granulometrias (material retido entre as peneiras ABNT 5-10; 10-20; 20-50 e < 50), três doses de escória, correspondentes a 0,00, 5,04 e 10,08 t ha-1, ou seja, 0,00, 1,01 e 2,02 g por copo com 0,40 dm³ de solo e duas testemunhas (escória e calcário dolomítico, na dose correspondente a V = 70 %, ou seja, 1,01 e 0,60 g por copo, respectivamente). Para definir as doses, adotou-se o método da saturação por bases, considerando-se o valor do PRNT da escória e do calcário, obtidos na granulometria correspondente. O solo foi mantido na capacidade de campo e incubado durante os períodos de três, seis e nove meses. As frações granulométricas da escória influiram diferentemente na acidez do solo. A fração retida entre as peneiras ABNT 5-10 mostrou-se ineficiente, enquanto a fração que passa pela peneira ABNT 50 foi a que conferiu o maior efeito na neutralização da acidez. A reatividade das partículas da escória retidas nas peneiras intermediárias, ABNT 10-20 e 20-50, foi proporcional aos valores vigentes na legislação brasileira para calcários. Portanto, a taxa de reatividade obtida para a escória foi de: ABNT nº 5-10 = 0 %; 10-20 = 22 %; 20-50 = 58 % e < 50 = 100 %.

Reciclagem química de Polietileno utilizando Sílica Mesoporosa tipo SBA-15 avalizada por Termogravimetriae Espectrometria de Massas

The chemical recycling of polyolefins has been the focus of increasing attention owing potential application as a fuel and as source chemicals. The use of plastic waste contributes to the solution of pollution problems.The use of catalysts can enhance the thermal degradation of synthetic polymers, which may be avaliated by Themogravimetry (TG) and mass spectrometry (MS) combined techniques. This work aims to propose alternatives to the chemistry recycling of low-density polyethylene (LDPE) on mesoporous silica type SBA-15 and AlSBA-15.The mesoporous materials type SBA-15 and AlSBA-15 were synthesized through the hydrothermal method starting from TEOS, pseudobohemite, cloridric acid HCl and water. As structure template was used Pluronic P123. The syntheses were accomplished during the period of three days. The best calcination conditions for removal of the organic template (P123) were optimized by thermal analysis (TG/DTG) and through analyses of Xray diffraction (XRD), infrared spectroscopy (FT-IR), nitrogen adsorption and scanning electron microscopy (SEM) was verified that as much the hydrothermal synthesis method as the calcination by TG were promising for the production of mesoporous materials with high degree of hexagonal ordination. The general analysis of the method of Analog Scan was performed at 10oC/min to 500 oC to avoid deterioration of capillary with very high temperatures. Thus, with the results, we observed signs mass/charge more evident and, using the MID method, was obtained curve of evolution of these signals. The addition of catalysis produced a decrease in temperature of polymer degradation proportional to the acidity of the catalyst. The results showed that the mesoporous materials contributed to the formation of compounds of lower molecular weight and higher value in the process of catalytic degradation of LDPE, representing an alternative to chemical recycling of solid waste

Strategy of specification of management areas: rice grain yield as related to soil fertility

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Amostragem do solo em área com cana-de-açúcar após aplicação de corretivos

Este trabalho objetivou avaliar o efeito de dois métodos de amostragem nas propriedades químicas do solo, em área com cana-de-açúcar após tratamentos corretivos de acidez. O primeiro método consistiu na amostragem de solo em 30% dos pontos na posição da linha e 70% na posição da entrelinha (LE). No segundo método, as amostras de solo foram coletadas em 100% dos pontos na posição da entrelinha (E) e da combinação de duas fontes de corretivos, escória e calcário, com níveis de correção do V% para 50, para 75 e para 100, e uma testemunha sem correção. A amostragem do solo pelo método LE superestimou a acidez potencial, enquanto a amostragem do solo na entrelinha apresentou melhor ajuste dos dados para determinação do pH, H + Al, Ca, Mg e V% do solo.

Efeito de lodo de esgoto na fertilidade de um Argissolo Vermelho-Amarelo cultivado com cana-de-açúcar

O objetivo deste trabalho foi avaliar os efeitos da aplicação de 0, 20 e 40 Mg ha-1 de lodo de esgoto, na presença e ausência de fertilizante mineral (NPK) na fertilidade e nos teores de metais pesados de um Argissolo Vermelho-Amarelo distrófico, cultivado com cana-de-açúcar. Amostras de solo foram coletadas aos 146, 272 e 484 dias após o plantio da cultura de cana-de-açúcar e foram submetidas à análise de fertilidade pelo método do Instituto Agronômico de Campinas, incluindo a determinação do S, Cr, Cd, Cu, Fe, Mn, Pb e Zn. O lodo de esgoto diminuiu a acidez do solo e forneceu Ca, P, S e Zn, principalmente. Seus efeitos foram de curta duração, restringindo-se a um ano agrícola. Os teores dos metais pesados das amostras de solo tratado foram maiores que os da testemunha, mas menores que os valores considerados perigosos ao ambiente.

Características físico-químicas de amidos modificados de grau alimentício comercializados no Brasil

Amidos nativos e modificados têm grande importância na indústria de alimentos, sendo empregados principalmente como espessantes e/ou estabilizantes. As limitações das pastas e géis obtidos a partir de amidos nativos tornaram necessário o desenvolvimento de muitos tipos de amidos modificados para aplicações alimentícias. Neste trabalho, algumas amostras de amidos modificados (n=20) disponíveis no Brasil foram recebidas de empresas produtoras e analisadas em relação a algumas características físico-químicas e propriedades tecnológicas. Um levantamento do uso de amidos modificados em alimentos também é apresentado, revelando crescente interesse pela indústria nesses ingredientes. Constatou-se que, enquanto alguns alimentos industrializados, como maioneses contêm em suas formulações amidos modificados, outros como condimento preparado de mostarda contêm apenas amido nativo. As análises físico-químicas permitiram concluir que alguns amidos modificados apresentavam teores elevados de acidez, relacionados à presença de reagentes utilizados em sua obtenção, não havendo presença de carboxilas nas suas macromoléculas. de maneira geral, os resultados de algumas propriedades tecnológicas avaliadas, tais como viscosidade aparente das pastas, resistência a congelamento/descongelamento e propriedade de expansão, estavam de acordo com a descrição dos produtos. As fontes mais observadas nas modificações foram, em ordem decrescente de importância, a mandioca, o milho ceroso e o milho regular.