Remoção de nitratos em água utilizando diferentes materiais e processos

The need to preserve the environment has led to the search for new materials for efficient disposal of chemical compounds that alter the stability of our natural resources. Among these resources, stands in first place the water, as a precious commodity and scarce, leading to the proper use and reuse. As a result, the World Health Organization has established maximum permissible values in drinking water, such as: 50 mg/L, 0, 1 mg/L and 0, 5 mg/L to at-3, at-2, NH 4, respectively. For these reasons, assesses the implementation of new materials and water treatment processes aiming at the removal of these compounds, such as alumina, in the form of powder or as a support for a catalytic system using inorganic membranes capable of supporting more severe conditions of temperature and pressure by opening new possibilities for applications of membrane reactors; and also for electrochemical treatments with doped diamond bobo electrodes (BDD) as anode and copper as cathode. For such purpose, was conducted the study of adsorption of nitrate in different times to assess the time required to achieve equilibrium by employing three commercial alumina called: acidic, basic and neutral alumina, with subsequent treatment only in the acidic alumina impregnating metals (PdCu/Al2O3) for the catalytic reaction. The materials were previously characterized by XRD, SEM techniques and ABET. Aluminas presented a considerable adsortive capacity of nitrate in the first thirty minutes, equivalent to 50% of removal reaching equilibrium in that time. After treatment, using alumina as catalyst for the reaction in batch reactor (Pd-Cu/Al2O3), the results were more favourable, totalling 64% reduction of ion NO3-at the end of three hours. On the other hand, the results for the catalytic reaction using the catalytic support Pd-Cu/TiO2 in membrane reactor proved to be low. -if, in this way, improve the conditions of catalytic system to optimize the process. Already, for the electrochemical tests using DDB1 electrodes as anode, and Cu, as cathode, there was a fairly significant nitrate reduction, approximately 80% of ion removal during three hours and cost viable applications.

Results of Closed-Flow Column Experiments (zip-archive 2.3 MB)

The identification of transport parameters by inverse modeling often suffers from equifinality or parameter correlation when models are fitted to observations of the solute breakthrough in column outflow experiments. This parameters uncertainty can be approached by the application of multiple experimental designs such as column experiments in open-flow mode and the recently proposed closed-flow mode. Latter are characterized by the recirculation of the column effluent into the solution supply vessel that feeds the inflow. Depending on the experimental conditions, the solute concentration in the solution supply vessel and the effluent follows a damped sinusoidal oscillation. As a result, the closed-flow experiment provides additional observables in the breakthrough curve. The evaluation of these emergent features allows intrinsic control over boundary conditions and impacts the uncertainty of parameters in inverse modeling. We present a comprehensive sensitivity analysis to illustrate the potential application of closed-flow experiments. We show that the sensitivity with respect to the apparent dispersion can be controlled by the experimenter leading to a decrease in parameter uncertainty as compared to classical experiments by an order of magnitude for optimal settings. With these finding we are also able to reduce the equifinality found for situations, where rate-limited interactions impede a proper determination of the apparent dispersion and rate coefficients. Furthermore, we show the expected breakthrough curve for equilibrium and kinetic sorption, the latter showing strong similarities to the behavior found for completely mixed batch reactor experiments. This renders the closed-flow mode a useful complementary approach to classical column experiments.

Production of bioplastics from hydrolysates of paper industry by Haloferax mediterranei

The biorefinery concept has attracted much attention over the last decade due to increasing concerns about the use of fossil resources. In this context emerged the use of bioplastics, namely polyhydroxyalkanoates (PHA). PHA are biocompatible and biodegradable plastics that can be obtained from renewable raw materials and can constitute an alternative solution to conventional plastics. In this work, hydrolysed cellulose pulp, coming from Eucalyptus globulus wood cooking, was used as substrate to the PHA-storing bacteria Haloferax mediterranei. The hydrolysed pulp is rich in simple sugars, mainly glucose (81.96 g.L-1) and xylose (20.90 g.L-1). Tests were made in defined medium with glucose and xylose and in hydrolysate supplemented with salts and yeast extract. Different concentrations of glucose were tested, namely 10, 15, 20, 30 and 40 g.L-1. The best accumulation results (27.1 % of PHA) were obtained in hydrolysate medium with 10 g.L-1. Using this concentration, assays were performed in fed-batch and sequencing batch reactor conditions in order to determine the best feeding strategy. The strategy that led to the best results was fed-batch assay with 24.7 % of PHA. An assay without sterile conditions was performed, in which was obtained the same growth than in sterilization test. Finally it was performed an assay in a bioreactor and a fast growth (0.14 h-1) with high glucose and xylose consumption rates (0.368 g.L-1.h-1 and 0.0947 g.L-1.h-1, respectively) were obtained. However 1.50 g.L-1 of PHA, corresponding to 16.1 % (92.52 % of 3HB and 3HV of 7.48 %) of % PHA were observed. The polymer was further characterized by DSC with a glass transition temperature of -6.07 °C, a melting temperature of 156.3 °C and a melting enthalpy of 63.07 J.g-1, values that are in accordance with the literature. This work recognizes for the first time the suitability of the pulp paper hydrolysate as a substrate for PHA production by H. mediterranei.

Eliminação/valorização de resíduos de frutas (kiwi) por digestão anaeróbia

Este estudo tem como objetivo a valorização económica de resíduos agroindustriais, nomeadamente resíduos de kiwi, por digestão anaeróbia de forma a otimizar a produção de biogás e a sua qualidade (% CH4). Trata-se de uma pesquisa experimental que consistiu na avaliação da produção de biogás usando diferentes proporções de substrato e inóculo, quatro valores distintos para a razão C:N, inóculo de diferentes digestores e colheita do inóculo em épocas distintas do ano. Os ensaios foram desenvolvidos num reator batch em condições mesofílicas, sendo o processo acompanhado por monitorização dos parâmetros: pH, Alcalinidade, Ácidos Gordos Voláteis (AGV), Sólidos Totais (ST), Sólidos Voláteis (SV), Carência Química de Oxigénio (CQO) e Carbono. Para a totalidade dos ensaios, o valor de pH no reator praticamente não apresentou variação, mantendo-se em torno de 7,0; a alcalinidade do meio, 1500 mg CaCO3/L, revelou-se adequada uma vez que no final do processo de DA a concentração de AGV (400-600 mg/L), nunca excede os valores considerados críticos. Os resultados obtidos apresentam valores interessantes para um número considerável de ensaios. Das 10 experiências realizadas, em duas foram obtidos resultados muito significativos em relação à literatura; o ensaio com 1% de substrato (experiência 2) registou uma produção de biogás de 1628 L/kg SV com uma %CH4 de 57% e o biogás de maior qualidade, 85% de metano, foi obtido no ensaio com 5% de resíduo de kiwi (experiência 10). As experiências em que se avaliou o efeito da razão C:N foram as menos produtivas, possivelmente devido à inibição da atividade da população microbiana pelo KNO3. A qualidade do inóculo revelou-se determinante num conjunto de ensaios, nomeadamente quando a sua colheita foi realizada no inverno, com o digestor a apresentar temperaturas bastante baixas. De acordo com os valores mais favoráveis para a produção de biogás, por tonelada de resíduo de kiwi poderá ser obtido um valor monetário bruto de 102 €, resolvendo-se um problema de eliminação deste resíduo, com valorização energética simultaneamente.

On The Use of Genetic Algorithms for Parameter Identification in Anaerobic Digestion Modelling

Anaerobic digestion (AD) of wastewater is a very interesting option for waste valorization, energy production and environment protection. It is a complex, naturally occurring process that can take place inside bioreactors. The capability of predicting the operation of such bioreactors is important to optimize the design and the operation conditions of the reactors, which, in part, justifies the numerous AD models presently available. The existing AD models are not universal, have to be inferred from prior knowledge and rely on existing experimental data. Among the tasks involved in the process of developing a dynamical model for AD, the estimation of parameters is one of the most challenging. This paper presents the identifiability analysis of a nonlinear dynamical model for a batch reactor. Particular attention is given to the structural identifiability of the model, which considers the uniqueness of the estimated parameters. To perform this analysis, the GenSSI toolbox was used. The estimation of the model parameters is achieved with genetic algorithms (GA) which have already been used in the context of AD modelling, although not commonly. The paper discusses its advantages and disadvantages.

Modelling of a batch sonochemical reactor

Ultrasonication of aqueous KI solution is known to yield I2 due to reaction of iodide ions with hydroxyl radicals, which in turn are generated due to cavitation. Based on this conceptual framework, a model has been developed to predict the rate of iodine formation for KI solutions of various concentrations under different gas atmospheres. The model follows the growth and collapse of a gas—vapour cavity using the Rayleigh—Plesset bubble dynamics equation. The bubble is assumed to behave isothermally during its growth phase and a part of the collapse phase. Thereafter it is assumed to collapse adiabatically, yielding high temperatures and pressures. Thermodynamic equilibrium is assumed in the bubble at the end of collapse phase. The contents of the bubble are assumed to mix with the liquid, and the reactor contents are assumed to be well stirred. The model has been verified by conducting experiments with KI solutions of different concentrations and using different gas atmospheres. The model not only explains these results but also the existence of a maximum when Ar---O2 mixtures of different compositions are employed.

Modelling of a batch sonochemical reactor

Ultrasonication of aqueous KI solution is known to yield I2 due to reaction of iodide ions with hydroxyl radicals, which in turn are generated due to cavitation. Based on this conceptual framework, a model has been developed to predict the rate of iodine formation for KI solutions of various concentrations under different gas atmospheres. The model follows the growth and collapse of a gas-vapour cavity using the Rayleigh-Plesset bubble dynamics equation. The bubble is assumed to behave isothermally during its growth phase and a part of the collapse phase. Thereafter it is assumed to collapse adiabatically, yielding high temperatures and pressures. Thermodynamic equilibrium is assumed in the bubble at the end of collapse phase. The contents of the bubble are assumed to mix with the liquid, and the reactor contents are assumed to be well stirred. The model has been verified by conducting experiments with KI solutions of different concentrations and using different gas atmospheres. The model not only explains these results but also the existence of a maximum when Ar-O2 mixtures of different compositions are employed.

Effect of agitation on the performance of an anaerobic sequencing batch biofilm reactor in the treatment of dairy effluents

Agitation rate is an important parameter in the operation of Anaerobic Sequencing Biofilm Batch Reactors (ASBBRs), and a proper agitation rate guarantees good mixing, improves mass transfer, and enhances the solubility of the particulate organic matter. Dairy effluents have a high amount of particulate organic matter, and their anaerobic digestion presents inhibitory intermediates (e. g., long-chain fatty acids). The importance of studying agitation in such batch systems is clear. The present study aimed to evaluate how agitation frequency influences the anaerobic treatment of dairy effluents. The ASBBR was fed with wastewater from milk pasteurisation process and cheese manufacture with no whey segregation. The organic matter concentration, measured as chemical oxygen demand (COD), was maintained at approximately 8,000 mg/L. The reactor was operated with four agitation frequencies: 500 rpm, 350 rpm, 200 rpm, and no agitation. In terms of COD removal efficiency, similar results were observed for 500 rpm and 350 rpm (around 90%) and for 200 rpm and no agitation (around 80%). Increasing the system`s agitation thus not only improved the global efficiency of organic matter removal but also influenced volatile acid production and consumption and clearly modified this balance in each experimental condition.

Coal desulfurization in a fluidized bed reactor

Fluidized bed reactor technology was investigated as a means of developing a new simple and low cost process for coal desulfurization. Preliminary experimental results obtained in a 2.54 cm batch fluidized bed reactor have shown that over 80% total sulfur reductions can be achieved by sequential chlorination and dechlorination/ hydrodesulfurization of high sulfur pulverized coals. Proximate and ultimate analyses of desulfurized coals have revealed enhanced carbon and fixed carbon levels and substantially reduced volatile, oxygen and hydrogen contents. While there was a minor increase in the ash content and heating value, nitrogen and chlorine contents were essentially unchanged. Compared to an earlier slurry phase process, the fluidized bed reactors process has specific advantages such as shorter reaction times, fewer processing steps and reduced reactant requirements. A fluidized bed reactor process may thus have a potential of being developed into a simple and economic means of converting high sulfur coals to environmentally acceptable fuels.

Near-complete transuranic waste incineration in a thorium fuelled pressurised water reactor

The production of long-lived transuranic (TRU) waste is a major disadvantage of fission-based nuclear power. Incineration, and virtual elimination, of waste stockpiles is possible in a thorium (Th) fuelled critical or subcritical fast reactor. Fuel cycles producing a net decrease in TRUs are possible in conventional pressurised water reactors (PWRs). However, minor actinides (MAs) have a detrimental effect on reactivity and stability, ultimately limiting the quality and quantity of waste that can be incinerated. In this paper, we propose using a thorium-retained-actinides fuel cycle in PWRs, where the reactor is fuelled with a mixture of thorium and TRU waste, and after discharge all actinides are reprocessed and returned to the reactor. To investigate the feasibility and performance of this fuel cycle an assembly-level analysis for a one-batch reloading strategy was completed over 125 years of operation using WIMS 9. This one-batch analysis was performed for simplicity, but allowed an indicative assessment of the performance of a four-batch fuel management strategy. The build-up of 233U in the reactor allowed continued reactive and stable operation, until all significant actinide populations had reached pseudo-equilibrium in the reactor. It was therefore possible to achieve near-complete transuranic waste incineration, even for fuels with significant MA content. The average incineration rate was initially around 330 kg per GW th year and tended towards 250 kg per GW th year over several decades: a performance comparable to that achieved in a fast reactor. Using multiple batch fuel management, competitive or improved end-of-cycle burn-up appears achievable. The void coefficient (VC), moderator temperature coefficient (MTC) and Doppler coefficient remained negative. The quantity of soluble boron required for a fixed fuel cycle length was comparable to that for enriched uranium fuel, and acceptable amounts can be added without causing a positive VC or MTC. This analysis is limited by the consideration of a single fuel assembly, and it will be necessary to perform a full core coupled neutronic-thermal-hydraulic analysis to determine if the design in its current form is feasible. In particular, the potential for positive VCs if the core is highly or locally voided is a cause for concern. However, these results provide a compelling case for further work on concept feasibility and fuel management, which is in progress. © 2011 Elsevier Ltd. All rights reserved.

Study on methane hydration process in a semi-continuous stirred tank reactor

The methane hydration process is investigated in a semi-continuous stirred tank reactor. Liquid temperatures and reaction rates without stirrer are compared with those occurring with stirrer, while at the same time better stirring conditions of the methane hydration process are given by the experiments. Some basic data of fluid mechanics, for example, stirring Reynolds number, Froucle number and stirrer power, are calculated during the methane hydration process, which can be applied to evaluate stirrer capacity and provide some basic data for a scaled up reactor. Based on experiment and calculations in this work, some conclusions are drawn. First, the stirrer has great influence on the methane hydration process. Batch stirring is helpful to improve the mass transfer and heat transfer performances of the methane hydration process. Second, induction time can be shortened effectively by use of the stirrer. Third, in this paper, the appropriate stirring velocity and stirring time were 320 rpm and 30 min, respectively, at 5.0 MPa, for which the storage capacity and reaction time were 159.1 V/V and 370 min, respectively. Under the condition of the on-flow state, the initial stirring Reynolds number of the fluid and the stirring power were 12,150 and 0.54 W, respectively. Fourth, some suggestions, for example, the use of another type of stirrer or some baffles, are proposed to accelerate the methane hydration process. Comparing with literature data, higher storage capacity and hydration rate are achieved in this work. Moreover, some fluid mechanics parameters are calculated, which can provide some references to engineering application.

Use of a batch rotating photocatalytic contactor for the degradation of organic pollutants in wastewater

Aqueous solutions of a chlorinated VOC, 3,4-dichlorobut-1-ene, as well as other pollutants, may be mineralised to carbon dioxide, water and hydrochloric acid using a sealed rotating photocatalytic reactor. The effect of pH, dissolved oxygen concentration, light intensity, pollutant concentration and rotation speed on the degradation rate have been investigated as well as competition kinetics with methanol. This reactor may be optimised to minimise competition effects in mixed solutions. (C) 2001 Elsevier Science B.V. All rights reserved.

Batch and continuous biogas production from grass silage liquor

Herein batch and continuous mesophilic anaerobic digestion of grass silage liquor was studied. The continuous process was carried out in Armfield digesters with an OLR ranging from 0.851 to 1.77 kg COD m-3 day-1. The effect of recirculation of effluent from the digester was investigated using different OLRs of grass silage liquor feed. These results showed that as the OLR increased, the methane yield decreased for the reactor with no recycle and increased for the reactor with recycle. However, the COD removal for both digesters was nearly the same at the same OLR. Overall these studies show that grass silage liquor can produce a high quality methane steam between 70% and 80% and achieve methane yields of 0.385 m3 kg-1 COD.

Moving from Batch to Continuous Operation for the Liquid Phase Dehydrogenation of Tetrahydrocarbazole

Despite the numerous advantages of continuous processing, high-value chemical production is still dominated by batch techniques. In this paper, we investigate options for the continuous dehydrogenation of 1,2,3,4- tetrahydrocarbazole using a trickle bed reactor operating under realistic liquid velocities with and without the addition of a hydrogen acceptor. Here, a commercial 5 wt % Pd/Al₂O₃ catalyst was observed to slowly deactivate, hence proving unsuitable for continuous use. This deactivation was attributed to the strong adsorption of a byproduct on the surface of the support. Application of a base washing technique resolved this issue and a stable continuous reaction has been demonstrated. As was previously shown for the batch reaction, the addition of a hydrogen acceptor gas (propene) can increase the overall catalytic activity of the system. 

Comparative effectiveness of solar disinfection using small-scale batch reactors with reflective, absorptive and transmissive rear surfaces

This study investigated the enhancement of solar disinfection using custom-made batch reactors with reflective (foil-backed) or absorptive (black-backed) rear surfaces, under a range of weather conditions in India. Plate counts of Escherichia coli ATCC11775 were made under aerobic conditions and under conditions where reactive oxygen species (ROS) were neutralised, i.e. in growth medium supplemented with 0.05% w/v sodium pyruvate plus incubation under anaerobic conditions. While the addition of either an absorptive or a reflective backing enhanced reactor performance under strong sunlight, the reflective reactor was the only system to show consistent enhancement under low sunlight, where the process was slowest. Counts performed under ROS-neutralised conditions were slightly higher than those in air, indicating that a fraction of the cells become sub-lethally injured during exposure to sunlight to the extent that they were unable to grow aerobically. However, the influence of this phenomenon on the dynamics of inactivation was relatively small