990 resultados para Subsuperficial acidity
Resumo:
The biodiesel is defined as the mono-alkyl ester derived from long-chain fatty acids, from renewable sources such as vegetable oils or animal fat, whose use is associated with the replacement of fossil fuels in diesel engine cycle. The biodiesel is susceptible to oxidation when exposed to air and this process of oxidation affects the quality of fuel, mainly due to long periods of storage. Because of this, the oxidation stability has been the focus of numerous researches since it directly affects the producers, distributors and users of fuel. One of the possibilities to increase the resistance of biodiesel is the autoxidation treatment with inhibitors of oxidation. The antioxidants can be used as potential inhibitors of the effects of oxidation on the kinematic viscosity and the index of acidity of biodiesel, thereby increasing oxidative stability. This work aims to examine the efficiency of antioxidants, α-tocopherol and butylated hydroxy-toluene (BHT), added the biodiesel content of remembrance through Pressurized-Differential Scanning Calorimetry (P-DSC), Thermogravimetry (TG) and Petrology. The results showed that the use of antioxidant BHT, at the concentration of 2000ppm, increased resistance to oxidation of the biodiesel and oxidative induction time (OIT), which is a better result as antioxidant than the α-tocopherol. With the thermogravimetric analysis, it was observed that the biodiesel presented an initial decomposition temperature of lower tendency than that of oil, demonstrating to be more volatile, bearing great similarity to the diesel and being characterized as an alternative fuel. The rheological analysis indicated that each sample of biodiesel behaved as a Newtonian fluid
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The present work reports the study of nanoporous structures, aiming at their use in research directed to the current demand of the petroleum industry to value heavy oil. Initially, two ways were chosen for the synthesis of porous structures from the molecular sieves of type Si-MCM-41. In the first way, the structure MCM-41 is precursory for heteroatom substitutes of silicon, generating catalyst of the type Al-MCM-41 from two different methods of incorporation of the metal. This variation of the incorporation method of Aluminum in the structure of Si-MCM-41 was carried out through the conventional procedure, where the aluminum source was incorporated to the gel of synthesis, and the procedure post-synthesis, where the Aluminum source was incorporated in catalyst after the synthesis of Si-MCM-41. In the second way, the MCM-41 acts as a support for growth of nanocrystals of zeolite embedded in their mesoporous, resulting in hybrid MCM-41/ZSM-5 catalyst. A comparative analysis was carried through characterizations by XRD, FTIR, measures of acidity through n-butylamine adsorption for TGA, SEM-XRF and N2 adsorption. Also crystalline aluminosilicate with zeolitic structure MFI of type ZSM-5 was synthesized without using organic templates. Methodologies to the preparation of these materials are related by literature using conventionally reactants that supply oxides of necessary silicon and aluminum, as well as a template agent, and in some cases co-template. The search for new routes of preparation for the ZSM-5 aimed at, above all, the optimization of the same as for the time and the temperature of synthesis, and mainly the elimination of the use of organic templates, that are material of high cost and generally very toxic. The current study is based on the use of the H2O and Na+ cations playing the role of structural template and charge compensation in the structure. Characterizations by XRD, FTIR, SEM-XRF and N2 adsorption were also conducted for this material in order to compare the samples of ZSM-5 synthesized in the absence of template and those used industrially and synthesized using structuring
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In last years it has talked a lot about the environment and the plastic waste produced and discarded. In last decades, the increasing development of research to obtain fuel from plastic material, by catalytic degradation, it has become a very attractive looking, as these tailings are discarded to millions worldwide. These materials take a long time to degrade themselves by ways said natural and burning it has not demonstrated a viable alternative due to the toxic products produced during combustion. Such products could bring serious consequences to public health and environment. Therefore, the technique of chemical recycling is presented as a suitable alternative, especially since could be obtain fractions of liquid fuels that can be intended to the petrochemical industry. This work aims to propose alternatives to the use of plastic waste in the production of light petrochemical. Zeolites has been widely used in the study of this process due to its peculiar structural properties and its high acidity. In this work was studied the reaction of catalytic degradation of high-density polyethylene (HDPE) in the presence HZSM-12 zeolites with different acid sites concentrations by thermogravimetry and pyrolysis coupled with GC-MS. The samples of the catalysts were mixed with HDPE in the proportion of 50% in mass and submitted to thermogravimetric analyses in several heating rates. The addition of solids with different acid sites concentrations to HDPE, produced a decrease in the temperature of degradation of the polymer proportional the acidity of the catalyst. These qualitative results were complemented by the data of activation energy obtained through the non-isothermal kinetics model proposed by Vyazovkin. The values of Ea when correlated to the data of surface acidity of the catalysts indicated that there is a exponential decrease of the energy of activation in the reaction of catalytic degradation of HDPE, in function of the concentration of acid sites of the materials. These results indicate that the acidity of the catalyst added to the system is one of the most important properties in the reaction of catalytic degradation of polyethylene
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In present work, mesoporous materials of the M41S family were synthesized, which were discovered in the early 90s by researchers from Mobil Oil Corporation, thus allowing new perspectives in the field of catalysis. One of the most important members of this family is the MCM-41, which has a hexagonal array of mesopores with pore diameters ranging from 2 to 10 nm and a high surface area, enabling it to become very promising for the use as a catalyst in the refining of oil in the catalytic cracking process, since the mesopores facilitate the access of large hydrocarbon molecules, thereby increasing the production of light products, that are in high demand in the market. The addition of aluminum in the structure of MCM-41 increases the acidity of the material, making it more beneficial for application in the petrochemical industry. The mesoporous materials MCM-41 and Al-MCM-41 (ratio Si / Al = 50) were synthesized through the hydrothermal method, starting with silica gel, NaOH and distilled water. CTMABr was used as template, for structural guiding. In Al-MCM-41 the same reactants were used, with the adding of pseudoboehmite (as a source of aluminum) in the synthesis gel. The syntheses were carried out over a period of four days with a daily adjustment of pH. The optimum conditions of calcination for the removal of the organic template (CTMABr) were discovered through TG / DTG and also through analysis by XRD, FTIR and Nitrogen Adsorption. It was found that both the method of hydrothermal synthesis and calcination conditions of the studies based on TG were promising for the production of mesoporous materials with a high degree of hexagonal array. The acidic properties of the materials were determined by desorption of n-butylamine via thermogravimetry. One proved that the addition of aluminum in the structure of MCM-41 promoted an increase in the acidity of the catalyst. To check the catalytic activity of these materials, a sample of Atmospheric Residue (RAT) that is derived from atmospheric distillation of oil from the Pole of Guamaré- RN was used. This sample was previously characterized by various techniques such as Thermogravimetry, FTIR and XRF, where through thermal analysis of a comparative study between the thermal degradation of the RAT, the RAT pyrolysis + MCM-41 and RAT + Al- MCM-41. It was found that the Al-MCM-41 was most satisfactory in the promotion of a catalytic effect on the pyrolysis of the RAT, as the cracking of heavy products in the waste occurred at temperatures lower than those observed for the pyrolysis with MCM-41, and thereby also decreasing the energy of activation for the process and increasing the rates of conversion of residue into lighter products
Resumo:
The catalytic processes play a vital role in the worldwide economy, a business that handles about US$ 13 billion per year because the value of products depends on the catalytic processes, including petroleum products, chemicals, pharmaceuticals, synthetic rubbers and plastics, among others. The zeolite ZSM-5 is used as catalyst for various reactions in the area petrochemical, petroleum refining and fine chemicals, especially the reactions of cracking, isomerization, alkylation, aromatization of olefins, among others. Many researchers have studied the hydrothermal synthesis of zeolite ZSM-5 free template and they obtained satisfactory results, so this study aims to evaluate the hydrothermal synthesis and the physicochemical properties of ZSM-5 with the presence and absence of template compared with commercial ZSM-5. The methods for hydrothermal synthesis of zeolite ZSM-5 are of scientific knowledge, providing the chemical composition required for the formation of zeolitic structure in the presence and absence of template. Samples of both zeolites ZSM-5 in protonic form were obtained by heat treatment and ion exchange, according to procedures reported in the literature. The sample of commercial ZSM-5 was acquired by the company Sentex Industrial Ltda. All samples were characterized by XRD, SEM, FTIR, TG / DTG / DSC, N2 adsorption and desorption and study of acidity by thermo-desorption of probe molecule (n-butylamine), in order to understand their physicochemical properties. The efficiency of the methods applied in this work and reported in the literature has been proved by well-defined structure of ZSM-5. According as the evaluation of physicochemical properties, zeolite ZSM-5 free template becomes promising for application in the refining processes or use as catalytic support, since its synthesis reduces environmental impacts and production costs
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TiTanate NanoTubes (TTNT) were synthesized by hydrothermal alkali treatment of TiO2 anatase followed by repeated washings with distinct degrees of proton exchange. TTNT samples with different sodium contents were characterized, as synthesized and after heattreatment (200-800ºC), by X-ray diffraction, scanning and transmission electron microscopy, electron diffraction, thermal analysis, nitrogen adsorption and spectroscopic techniques like FTIR and UV-Vis diffuse reflectance. It was demonstrated that TTNTs consist of trititanate structure with general formula NaxH2−xTi3O7·nH2O, retaining interlayer water in its multiwalled structure. The removal of sodium reduces the amount of water and contracts the interlayer space leading, combined with other factors, to increased specific surface area and mesopore volume. TTNTs are mesoporous materials with two main contributions: pores smaller than 10 nm due to the inner volume of nanotubes and larger pores within 5-60 nm attributed to the interparticles space. Chemical composition and crystal structure of TTNTs do not depend on the average crystal size of the precursor TiO2-anatase, but this parameter affects significantly the morphology and textural properties of the nanostructured product. Such dependence has been rationalized using a dissolution-recrystallization mechanism, which takes into account the dissolution rate of the starting anatase and its influence on the relative rates of growth and curving of intermediate nanosheets. The thermal stability of TTNT is defined by the sodium content and in a lower extent by the crystallinity of the starting anatase. It has been demonstrated that after losing interlayer water within the range 100-200ºC, TTNT transforms, at least partially, into an intermediate hexatitanate NaxH2−xTi6O13 still retaining the nanotubular morphology. Further thermal transformation of the nanostructured tri- and hexatitanates occurs at higher or lower temperature and follows different routes depending on the sodium content in the structure. At high sodium load (water washed samples) they sinter and grow towards bigger crystals of Na2Ti3O7 and Na2Ti6O13 in the form of rods and ribbons. In contrast, protonated TTNTs evolve to nanotubes of TiO2(B), which easily convert to anatase nanorods above 400ºC. Besides hydroxyls and Lewis acidity typical of titanium oxides, TTNTs show a small contribution of protonic acidity capable of coordinating with pyridine at 150ºC, which is lost after calcination and conversion into anatase. The isoeletric point of TTNTs was measured within the range 2.5-4.0, indicating behavior of a weak acid. Despite displaying semiconductor characteristics exhibiting typical absorption in the UV-Vis spectrum with estimated bandgap energy slightly higher than that of its TiO2 precursor, TTNTs showed very low performance in the photocatalytic degradation of cationic and anionic dyes. It was concluded that the basic reason resides in its layered titanate structure, which in comparison with the TiO2 form would be more prone to the so undesired electron-hole pair recombination, thus inhibiting the photooxidation reactions. After calcination of the protonated TTNT into anatase nanorods, the photocatalytic activity improved but not to the same level as that exhibited by its precursor anatase
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A partially hydrolyzed polyacrylamide (HPAM) is a copolymer composed of acrylamide and sodium acrylate. Due to its wide range of applications there are different methods for its quantification and characterization in solution systems. Evaluation of C* is important to describe the transition from dilute to semi-dilute, behavior, when the solution will have its characteristic viscosity at concentrations above C*. This dissertation describes the determination of the critical concentration of overlap C* by potentiometry of partially hydrolyzed polyacrylamide - HPAM under acidic conditions. Based on the law of mass action and the proper treatment of the constant of aggregate formation, polymer molecular weight, degree of polymerization and hydrolysis were calculated. The inflection point was determined by the intersection of the resulting equation and mathematical development, statistically satisfy the experimental points relating the number of moles of monomers (n), equilibrium constant of formation of the entanglements (K*), pH, C* and acidity constant of the polymer (Ka). The viscometric parameters of C* showed a percentage difference compared to potentiometers. The results for the determination of C*, and degree of copolymerization molar mass proved to be a simple alternative for the characterization of polymers with protonated monomers and water soluble
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The aim of this study was to evaluate the potential of near-infrared reflectance spectroscopy (NIRS) as a rapid and non-destructive method to determine the soluble solid content (SSC), pH and titratable acidity of intact plums. Samples of plum with a total solids content ranging from 5.7 to 15%, pH from 2.72 to 3.84 and titratable acidity from 0.88 a 3.6% were collected from supermarkets in Natal-Brazil, and NIR spectra were acquired in the 714 2500 nm range. A comparison of several multivariate calibration techniques with respect to several pre-processing data and variable selection algorithms, such as interval Partial Least Squares (iPLS), genetic algorithm (GA), successive projections algorithm (SPA) and ordered predictors selection (OPS), was performed. Validation models for SSC, pH and titratable acidity had a coefficient of correlation (R) of 0.95 0.90 and 0.80, as well as a root mean square error of prediction (RMSEP) of 0.45ºBrix, 0.07 and 0.40%, respectively. From these results, it can be concluded that NIR spectroscopy can be used as a non-destructive alternative for measuring the SSC, pH and titratable acidity in plums
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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
Resumo:
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
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The pulps are products that add economic value enjoy the fruits of the surplus productions of the same. Have good market acceptance because of its practicality and diversity of flavors available year round. In order to assess the quality of the fruit pulp through the physical and chemical parameters and the characteristics of manufacturing industry, we analyzed 36 samples of frozen fruit pulp of three brands marketed in RIO Grande do Norte, 14 brand A, 12 of 10 brand B and brand C, which corresponded to 14 different flavors, of which 10 have identity Standards and Quality (ISQ S) established by the Ministério da Agricultura, Pecuária e Abastecimento (MAPA), totaling 27 samples with ISQ s. We conducted the following physicalchemical analyzes on samples of fruit pulp: Total solids, total soluble solids, pH, titratable acidity, total sugars and the determination of ascorbic acid. The percentage of failure for each parameter evaluated was 37, 04% in total soluble solids, 22,22% for total solids and titratable acidity, 7,40% in relation to pH. The total sugars were within the requirements demanded by the MAPA and ascorbic acid content, determined only in the pulp of acerola and cashew, presented a non compliance in the pulp of brand B. The percentage of failures of the pulps with ISQ S was 59% with brand A, B and C accounted for 3,70%, 33,33% and 22,22% respectively. The pulps which have no established atandards such as pineapple pulp, showed similar values between brands and literature data unlike the pulp of plum, jackfruit and tamarind which diverged greatly in parameters such as total solids and total soluble solids. The study demonstrates the need for greater quality control by the producers with respect to raw materials, processing, packing, stored and the importance of ISQ S to establish the flavors have not yet covered by existing legislation, but already highly commercialized
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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
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A adubação é um dos fatores que influem na produção e qualidade dos frutos; portanto, a necessidade de se estudar o efeito do nitrogênio aplicado antes e após a indução floral nestas características dos frutos de abacaxi é fundamental. Os objetivos deste trabalho foram avaliar a produtividade, o estado nutricional e os aspectos quantitativos e qualitativos dos frutos de abacaxizeiro 'Smooth Cayenne' submetidos a doses e parcelamentos do nitrogênio, cultivado em Guaraçaí-SP. O delineamento experimental adotado foi o de blocos ao caso, com quatro repetições e dezesseis tratamentos, num esquema fatorial 4x4, sendo quatro doses de N: 7,5; 15; 22,5 e 30 g planta-1 de N, e quatro parcelamentos: toda a dose aplicada antes da indução floral, metade da dose antes da indução floral e a outra metade após a indução, 2/3 da dose antes da indução e 1/3 da dose após a indução e toda a dose após a indução floral. A aplicação total do N após a indução floral, independentemente da dose, resultou em menores teores foliares de N e dimensões da folha D, apresentando na colheita frutos pequenos, com menor índice de maturação e maior acidez. Para obtenção de frutos de abacaxi cv. Smooth Cayenne, com maior tamanho, massa e maior teor de SST e menor acidez, a adubação nitrogenada pode ser aplicada em dose total, antes da indução floral, ou parcelada 2/3 antes e 1/3 após esta indução. A adubação nitrogenada incrementou os teores foliares de N, entretanto não teve efeito nas dimensões, produtividade e qualidade de frutos de abacaxizeiro cv. Smooth Cayenne.
Resumo:
Poucos são os estudos desenvolvidos com a aplicação via foliar de micronutrientes, na cultura do abacaxi. Este trabalho teve como objetivo avaliar os efeitos de B e Zn, em forma de quelato, ácido ou sal, via foliar, buscando-se obter respostas sobre os efeitos na produtividade e qualidade dos frutos. O experimento foi realizado em Guaraçaí (SP), em solo com textura média. Foram utilizadas mudas tipo filhote, da cultivar Smooth Cayenne (Havaiano). O delineamento experimental adotado foi o de blocos ao acaso, com quatro repetições, utilizando-se fontes para fornecer, em cada aplicação, 110 g ha-1de B e 250 g ha-1de Zn. Foram realizadas duas pulverizações foliares, aos 7 e 9 meses após o plantio. As fontes de B e Zn não exerceram efeito nos teores de sólidos solúveis totais, acidez titulável, diâmetro médio do fruto, comprimento do fruto sem coroa e índice de maturação. Apenas os teores de B, Zn e K, na folha, foram influenciados pelos tratamentos utilizados.
Resumo:
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.