Estudo de titanatos nanoestruturados obtidos por tratamento hidrotérmico de óxido de titânio em meio alcalino

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

Caracterização de poliacrilamida parcialmente hidrolisada em regime concentrado

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

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

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

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

Caracterização física e sensorial do café produzido nas condições topoclimáticas de Jesuitas, Paraná

Climatic variations influence formation and maturation of coffee grains by altering their intrinsic characteristics, which call allow for several types of coffee qualities, including the potential for production of special coffee. This study was carried out to verify the effect of environmental conditions and crop cultivation on chemical composition and their consequences in cup quality of coffees from region of Jesuitas, Parana State. During the same crop season this study was accomplished (2002-2003), cup quality was evaluated among the producers in several coffee-growing municipalities in Parana State. It was observed that 86% of samples were classified simply as "soft" (smooth flavor) or "hard" (bolder flavor), and 14% were classified as rioysh/rio (strong unpleasant taste). The results concluded that the practices adopted by producers, who have collaborated with the study, reflected positively oil the final cup quality, when compared to the overall quality results in the State. The climatic conditions and practices of crop management and harvest ill the Jesuitas region made for bolder coffee with low acidity, comparable to high quality coffees produced in Brazil and abroad.

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 residual da escória de siderurgia como corretivo de acidez do solo na soqueira de cana-de-açúcar

A escória de siderurgia, como material corretivo e efeito residual prolongado, pode beneficiar culturas de ciclo longo, a exemplo da cana-de-açúcar, minimizando a queda de produção ao longo do ciclo produtivo. Este trabalho objetivou avaliar diferentes níveis de saturação por bases, utilizando, como corretivo do solo, a escória de siderurgia, comparando-a com calcário calcítico, nas alterações de alguns atributos químicos do solo, bem como na resposta da soqueira da cana-de-açúcar. Para isto, realizou-se um experimento com a variedade SP 80-1842, durante o terceiro e o quarto corte, nos anos agrícolas 2000/01 e 2001/02. Os tratamentos, dispostos em blocos casualizados, em esquema fatorial com quatro repetições, constaram de duas fontes de corretivos, calcário calcítico e escória de siderurgia, e quatro níveis de correção, estimados pelo método da saturação por bases (V %): testemunha (sem correção) e com correção para V % de 50; 75 e 100, tendo sido tais corretivos aplicados na época do plantio da cana-de-açúcar. O calcário calcítico e a escória de siderurgia promoveram efeito residual benéfico, após 48 meses da aplicação, na correção da acidez do solo e na elevação do valor da saturação por bases; a maior dose de calcário causou efeito depressivo no perfilhamento, no número de colmos industrializáveis e na produção da cana-de-açúcar, fato não observado com uso da escória de siderurgia; a aplicação da escória de siderurgia e do calcário, em pré-plantio, promoveu efeito residual positivo na produção da soqueira de cana-de-açúcar.

Vida-de-prateleira de goiabas, cv. Sassaoka, minimamente processadas e armazenadas em diferentes embalagens

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