Oxidação úmida de fenóis com catalisadores de ferro suportado em argilominerais em reator de leito de lama (slurry)

The wet oxidation of organic compounds with CO2 and H2O has been demonstrated to be an efficient technique for effluent treatment. This work focuses on the synthesis, characterization and catalytic performance of Fe-MnO2/CeO2, K-MnO2/CeO2/ palygorskite and Fe/ palygorskite toward the wet oxidative degradation of phenol. The experiments were conducted in a sludge bed reactor with controlled temperature, pressure and stirring speed and sampling of the liquid phase. Experiments were performed on the following operating conditions: temperature 130 ° C, pressure 20.4 atm, catalyst mass concentration of 5 g / L initial concentration of phenol and 0.5 g / L. The catalytic tests were performed in a slurry agitated reactor provided with temperature, pressure and agitation control and reactor liquid sampling. The influences of iron loaded on the support (0.3; 7 and 10%, m/m) and the initial pH of the reactant medium (3.1; 6.8; 8.7) were studied. The iron dispersion on the palygorskite, the phase purity and the elemental composition of the catalyst were evaluated by X-Ray Difraction (XRD), Scanning Electron Microscopy (SEM) and X-Ray Flourescence (XRF). The use of palygorskite as support to increase the surface area was confirmed by the B.E.T. surface results. The phenol degradation curves showed that the Fe3+ over palygorskite when compared with the other materials tested has the best performance toward the (Total Organic carbonic) TOC conversion. The decrease in alkalinity of the reaction medium also favors the conversion of TOC. The maximum conversion obtained from the TOC with the catalyst 3% Fe / palygorskite was around 95% for a reaction time of 60 minutes, while reducing the formation of acids, especially acetic acid. With products obtained from wet oxidation of phenol, hydroquinone, p-benzoquinone, catechol and oxalic acid, identified and quantified by High Performance Liquid Chromatography was possible to propose a reaction mechanism of the process where the phenol is transformed into the homogeneous and heterogeneous phase in the other by applying a kinetic model, Langmuir-Hinshelwood type, with evaluation of kinetic constants of different reactions involved.

Avaliação e modelagem da absorção de H2S do gás natural em coluna de leito estagnado

Natural gas, although basically composed by light hydrocarbons, also presents contaminant gases in its composition, such as CO2 (carbon dioxide) and H2S (hydrogen sulfide). The H2S, which commonly occurs in oil and gas exploration and production activities, causes damages in oil and natural gas pipelines. Consequently, the removal of hydrogen sulfide gas will result in an important reduction in operating costs. Also, it is essential to consider the better quality of the oil to be processed in the refinery, thus resulting in benefits in economic, environmental and social areas. All this facts demonstrate the need for the development and improvement in hydrogen sulfide scavengers. Currently, the oil industry uses several processes for hydrogen sulfide removal from natural gas. However, these processes produce amine derivatives which can cause damage in distillation towers, can cause clogging of pipelines by formation of insoluble precipitates, and also produce residues with great environmental impact. Therefore, it is of great importance the obtaining of a stable system, in inorganic or organic reaction media, able to remove hydrogen sulfide without formation of by-products that can affect the quality and cost of natural gas processing, transport, and distribution steps. Seeking the study, evaluation and modeling of mass transfer and kinetics of hydrogen removal, in this study it was used an absorption column packed with Raschig rings, where the natural gas, with H2S as contaminant, passed through an aqueous solution of inorganic compounds as stagnant liquid, being this contaminant gas absorbed by the liquid phase. This absorption column was coupled with a H2S detection system, with interface with a computer. The data and the model equations were solved by the least squares method, modified by Levemberg-Marquardt. In this study, in addition to the water, it were used the following solutions: sodium hydroxide, potassium permanganate, ferric chloride, copper sulfate, zinc chloride, potassium chromate, and manganese sulfate, all at low concentrations (»10 ppm). These solutions were used looking for the evaluation of the interference between absorption physical and chemical parameters, or even to get a better mass transfer coefficient, as in mixing reactors and absorption columns operating in counterflow. In this context, the evaluation of H2S removal arises as a valuable procedure for the treatment of natural gas and destination of process by-products. The study of the obtained absorption curves makes possible to determine the mass transfer predominant stage in the involved processes, the mass transfer volumetric coefficients, and the equilibrium concentrations. It was also performed a kinetic study. The obtained results showed that the H2S removal kinetics is greater for NaOH. Considering that the study was performed at low concentrations of chemical reagents, it was possible to check the effect of secondary reactions in the other chemicals, especially in the case of KMnO4, which shows that your by-product, MnO2, acts in H2S absorption process. In addition, CuSO4 and FeCl3 also demonstrated to have good efficiency in H2S removal