Ação promotora do berílio em catalisadores da síntese do estireno

The catalytic dehydrogenation of ethylbenzene in presence of steam is the main commercial route to produce styrene. The industrial catalysts are potassium- and chromia-doped hematite which show low surface areas leading to bad performance and short life. In order to develop catalysts with high areas, the effect of beryllium on the textural properties and on the catalytic performance of this iron oxide was studied. The influence of the amount of the dopant, the starting material and the calcination temperature were also studied. In sample preparations, iron and beryllium salts (nitrate or sulfate) were hydrolyzed with ammonia and then calcinated. The experiments followed a factorial design with two variables in two levels (Fe/Be= 3 and 7; calcination temperature= 500 and 700ºC). Solids without any dopant were also prepared. Samples were characterized by elemental analysis, infrared spectroscopy, surface area and porosity measurements, X-ray diffraction, DSC and TG. The catalysts were tested in a microreactor at 524ºC and 1 atm, by using a mole ratio of steam/ ethylbenzene=10. The selectivity was measured by monitoring styrene, benzene and toluene formation. It was found that the effect of beryllium on the characteristics of hematite and on its catalytic performance depends on the starting material and on the amount of dopant. Surface areas increased due to the dopant as well as the nature of the precursor; samples produced by beryllium sulfate showed higher areas. Beryllium-doped solids showed a higher catalytic activity when compared to pure hematite, but no significant influence of the anion of starting material was noted. It can be concluded that beryllium acts as both textural and structural promoter. Samples with Fe/Be= 3, heated at 500ºC, lead to the highest conversion and were the most selective. However, catalysts prepared from beryllium sulfate are the most promising to ethylbenzene dehydrogenation due to their high surface area which could lead to a longer life.

The impact of bioavailability limitations on microbial stable isotope fractionation in a multiphase system

Stable isotope fractionation analysis of contaminants is a promising method for assessing biodegradation of contaminants in natural systems. However, standard procedures to determine stable isotope fractionation factors, so far, neglect the influence of pollutant bioavailability on stable isotope fractionation. On a microscale, bioavailability may vary due to the spatio-temporal variability of local contaminant concentrations, limited effective diffusivities of the contaminants and cell densities, and thus, the pollutant supply might not meet the intrinsic degradation capacity of the microorganisms. The aim of this study was to demonstrate the effect of bioavailability on the apparent stable isotope fractionation, using a multiphase laboratory setup. The data gained show that the apparent isotope fractionation factors observed during biodegradation processes depend on the amount of biomass and/or the rate of toluene mass transfer from a second to the aqueous phase. They indicate that physico-chemical processes need to be taken into account when stable isotope fractionation analysis is used for the quantification of environmental contaminant degradation.

Desproporcionamento de tolueno sobre zeólitas tipo mordenita - atividade e seletividade na obtenção de xilenos

A sodium mordenite zeolite (Na-MOR) was synthesized and modified by dealumination with chloridric acid solution (H-MOR). X-Ray Diffraction (XRD), Inductive Coupled Plasm (ICP) and Scanning Electron Micrograph (SEM) techniques were used for sample characterization. The zeolite catalytic behavior was evaluated through toluene disproportionation at 435°C. It was verified that mordenites were very selective for the disproportionation reaction and the samples with higher aluminum content showed larger initial activity, however, these samples showed too a higher deactivation velocity due to a blockage of the unidimensional porous system of the zeolite by coke deposits. The selectivity to xylene isomers was practically not influenced by the Si/Al ratio and changed with the time on stream, due to coke formation. Transition state shape selectivity inside the mordenite pores is also discussed.

Evaluation of potential breath biomarkers for active smoking: assessment of smoking habits

Different compounds have been reported as biomarkers of a smoking habit, but, to date, there is no appropriate biomarker for tobacco-related exposure because the proposed chemicals seem to be nonspecific or they are only appropriate for short-term exposure. Moreover, conventional sampling methodologies require an invasive method because blood or urine samples are required. The use of a microtrap system coupled to gas chromatography–mass spectrometry analysis has been found to be very effective for the noninvasive analysis of volatile organic compounds in breath samples. The levels of benzene, 2,5-dimethylfuran, toluene, o-xylene, and m- p-xylene have been analyzed in breath samples obtained from 204 volunteers (100 smokers, 104 nonsmokers; 147 females, 57 males; ages 16 to 53 years). 2,5-Dimethylfuran was always below the limit of detection (0.005 ppbv) in the nonsmoker population and always detected in smokers independently of the smoking habits. Benzene was only an effective biomarker for medium and heavy smokers, and its level was affected by smoking habits. Regarding the levels of xylenes and toluene, they were only different in heavy smokers and after short-term exposure. The results obtained suggest that 2,5-dimethylfuran is a specific breath biomarker of smoking status independently of the smoking habits (e.g., short- and long-term exposure, light and heavy consumption), and so this compound might be useful as a biomarker of smoking exposure

Comparação entre injeção na coluna ("on-column") e headspace dinâmico na determinação de benzeno, tolueno e xilenos (BTX) em amostras de água

The analysis of water samples containing volatile organic compounds has become an important task in analytical chemistry. Gas chromatography has been widely used for the analysis of volatile organic compounds in water. The headspace analysis shows as a principal characteristic the possibility of determination of the volatile components in drinking water. Benzene, Toluene and Xylene (BTX) are important compounds usually present in drinking water, from contamination by petroleum derivatives. Since they are toxic compounds even when present in low concentration levels, their determination is important in order to define the quality of the water. The sampling technique using headspace, coupled with gas chromatography as the separation method, showed to be suitable for BTX analysis in several samples at the mug/L (ppb) level.

Efeito da concentração do catalisador acetilacetonato férrico na cura de poliuretano à base de polibutadieno líquido hidroxilado (PBLH) e diisocianato de isoforona (IPDI)

The reaction between hydroxy-terminated polybutadiene and isophorone diisocyanate constitutes the base of the curing process of the most composite solid propellant used in the propulsion of solid rocket propellant. In this work, differential scanning calorimetry and viscosity measurements were used to evaluate the effect of the ferric acetylacetonate catalyst concentration on the reaction between HTBR and IPDI. These analyses show one exotherm, which shifts to lower temperatures as the catalyst concentration increases. The viscosity analyses show that the increase of temperature causes, at first, a reduction in the mixture viscosity, reaching a minimum range called gelification region (increasing the crosslinking density).

Exposição ocupacional a compostos orgânicos voláteis na indústria naval

The scope of this study involved the evaluation of the concentration of some volatile organic compounds in the internal environmental air of a naval shipyard in the State of Rio de Janeiro, during painting activities in enclosed, semi-enclosed and open areas. Xylene was the volatile compound found in greatest abundance (25.20 to 191.66 ppm) in the locations researched. Benzene in the air, which is a carcinogenic substance, attained levels of 3.34 ppm in semi-enclosed environments and the highest levels of toluene, xylene and n-butanol were found in the enclosed space of the ship. Results obtained highlight the need to establish air quality control programs in these internal areas, in order to safeguard the health of the workers.

Determinação da massa molar por crioscopia: terc-butanol, um solvente extremamente adequado

We intend to divulge an easy experiment that permits the determination of molar masses of various compounds by cryoscopy. The major advantage of this is the use of the tert-butyl alcohol as a solvent, which requires simple apparatus and easy procedures. The melting point of this alcohol is around 25 ºC, which makes it easy to freeze and then melt the solutions. This solvent has a high cryoscopic constant and is miscible with both polar and non-polar compounds. The molar masses of acetone, water, chloroform, dichloro-methane, ethanol, hexane, carbon tetrachloride and toluene were determined. The results were good except for water. Even though there are reliable techniques of molar mass determination nowadays, this method is still frequently taught in undergraduate courses.

Reaction Kinetics and Viscosity Modelling in the Fusion Syntheses of Ca- and Ca/Mg-resinates

Rosin is a natural product from pine forests and it is used as a raw material in resinate syntheses. Resinates are polyvalent metal salts of rosin acids and especially Ca- and Ca/Mg- resinates find wide application in the printing ink industry. In this thesis, analytical methods were applied to increase general knowledge of resinate chemistry and the reaction kinetics was studied in order to model the non linear solution viscosity increase during resinate syntheses by the fusion method. Solution viscosity in toluene is an important quality factor for resinates to be used in printing inks. The concept of critical resinate concentration, c crit, was introduced to define an abrupt change in viscosity dependence on resinate concentration in the solution. The concept was then used to explain the non-inear solution viscosity increase during resinate syntheses. A semi empirical model with two estimated parameters was derived for the viscosity increase on the basis of apparent reaction kinetics. The model was used to control the viscosity and to predict the total reaction time of the resinate process. The kinetic data from the complex reaction media was obtained by acid value titration and by FTIR spectroscopic analyses using a conventional calibration method to measure the resinate concentration and the concentration of free rosin acids. A multivariate calibration method was successfully applied to make partial least square (PLS) models for monitoring acid value and solution viscosity in both mid-infrared (MIR) and near infrared (NIR) regions during the syntheses. The calibration models can be used for on line resinate process monitoring. In kinetic studies, two main reaction steps were observed during the syntheses. First a fast irreversible resination reaction occurs at 235 °C and then a slow thermal decarboxylation of rosin acids starts to take place at 265 °C. Rosin oil is formed during the decarboxylation reaction step causing significant mass loss as the rosin oil evaporates from the system while the viscosity increases to the target level. The mass balance of the syntheses was determined based on the resinate concentration increase during the decarboxylation reaction step. A mechanistic study of the decarboxylation reaction was based on the observation that resinate molecules are partly solvated by rosin acids during the syntheses. Different decarboxylation mechanisms were proposed for the free and solvating rosin acids. The deduced kinetic model supported the analytical data of the syntheses in a wide resinate concentration region, over a wide range of viscosity values and at different reaction temperatures. In addition, the application of the kinetic model to the modified resinate syntheses gave a good fit. A novel synthesis method with the addition of decarboxylated rosin (i.e. rosin oil) to the reaction mixture was introduced. The conversion of rosin acid to resinate was increased to the level necessary to obtain the target viscosity for the product at 235 °C. Due to a lower reaction temperature than in traditional fusion synthesis at 265 °C, thermal decarboxylation is avoided. As a consequence, the mass yield of the resinate syntheses can be increased from ca. 70% to almost 100% by recycling the added rosin oil.

Natureza do coque formado sobre a mordenita durante a transalquilação de benzeno

Zeolite catalysts have been extensively used in petroleum refining and the chemical industry although they are deactivated by coke deposition. In order to find the best condition to avoid deactivation, the coke formation on H-mordenite was studied in this work. The coke was produced during benzene transalkylation with C9+ aromatics, under several reaction conditions. It was found that hydrogenated coke was produced in all samples without affecting the selectivity of toluene and xylene formation. This is explained in terms of the mordenite structure and the presence of hydrogen.

Contaminação de águas por BTXs e processos utilizados na remediação de sítios contaminados

After decades of polluting actions the environment manifests serious and global consequences. The contamination of soils and groundwater by organic compounds is a widespread problem mainly on account of contamination by leakage from underground storage tanks, which often results in the release of gasoline or other chemicals. The main problem about groundwater contamination is due to the toxicity of water-soluble components such as benzene, toluene and xylene (BTX). In the present work a study about classical and modern methods for remediation of BTX is reported.

Efeito do cromo nas propriedades catalíticas da MCM-41

The effect of chromium on the catalytic properties of MCM-41 was evaluated in order to develop new catalysts for the trimethylbenzene transalkylation with benzene to produce ethylbenzene, a high-value aromatic in the industry. It was found that chromium decreases the specific surface area but increases the acidity, turning MCM-41 into an active and selective catalyst for ethylbenzene and toluene production. The coke produced on the catalyst is hydrogenated and mainly located outside the pores and thus can be easily removed. The catalyst is more active and selective than mordenite, a commercial catalyst, and thus more promising for commercial applications.

Degradação de BTXs via processos oxidativos avançados

In this study the efficiency of advanced oxidative processes (AOPs) were investigated toward the degradation of aqueous solutions containing benzene, toluene and xylenes (BTX). The results indicated that BTX can be effectively oxidized by the UV-A-assisted photo-Fenton process. The treatment permits almost total degradation of BTX and removal of more than 80% of the phenolyc intermediates at reaction times of about 30 min. Preliminary investigations using solar light suggest a good potentiality of the process for the treatment of large volumes of aqueous samples containing these polluting species.

A convenient method for the determination of moisture in aromatic plants

A method is proposed for the determination of the moisture content of aromatic plants. This method is based on the co-distillation of the starting material in a modified Clevenger apparatus with four organic solvents (toluene, cyclohexane, dichloromethane and carbon tetrachloride). The results were compared with those obtained by oven drying at 105 ºC and steam distillation of the essential oil. The efficiencies of the methods were shown to be equivalent. The solvent distillation method was more practical, especially with respect to operating time (2 h).

Caracterização química do "pitch" em indústria de celulose e papel de Eucalyptus

The chemical analysis of the acetone, chloroform, toluene and methanol extracts of a pitch sample was carried out by IR and GC-MS, leading to the identification of sixty nine compounds, including fatty acids, alcohols and hydrocarbons. Analysis of the acetone extractive of a eucalyptus wood used in Brazil for pulp production was also carried out, resulting in identification of fifty nine compounds, including mainly fatty acids, phenolic compounds, beta-sitosterol and other steroids. This analysis showed that pitch formation had a contribution from wood extractives and other sources of contamination. The results obtained and the methodology applied can be used by the pulp industry to develop new methods of pitch control.