Characteristics of Dielectric Barrier Discharge Reactor for Material Treatment

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

ASSESSMENT of POLYATOMIC INTERFERENCES ELIMINATION USING A COLLISION REACTION INTERFACE (CRI) FOR INORGANIC ANALYSIS of FUEL ETHANOL BY ICP-QMS

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

Electrocoagulation/flotation followed by fluidized bed anaerobic reactor applied to tannery effluent treatment

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

Use of sorghum seed tissue as a biocatalyst in a stirred reactor for oxalic acid determination

The enzyme oxalate oxidase, E.C. 1.2.3.4 from Sorghum vulgare seeds (variety BR303) was used to develop a new sensor for oxalate determination without any purification. The sorghum seeds were conditioned in a 0.10 mol I-1 KCl solution. Then, these seeds were put in a stirring bar type enzymic reactor and coupled with an electrode for CO2. This device was introduced into a cell containing 10.0 ml of a 0.10 mol I-1 KCl solution saturated with oxygen. This sensor showed a linear response between 1.0 and 4.0 × 10-3 mol I-1 with a slope of 30 mV per decade of oxalate concentration at 25.0°C. The sensor was stable for one month or 200 determinations. The response time was about 60 s. The Michaelis-Menten constant determined for this enzyme was 1.5 × 10-3 mol I-1.

Determination of Oxalate in Grass by FIA with a Spectrophotometric Detection System Using a Two Enzyme Reactor

A new methodology for soluble oxalic acid determination in grass samples was developed using a two enzyme reactor in an FIA system. The reactor consisted of 3 U of oxalate oxidase and 100 U of peroxidase immobilized on Sorghum vulgare seeds activated with glutaraldehyde. The carbon dioxide was monitored spectrophotometrically, after reacting with an acid-base indicator (Bromocresol Purple) after it permeated through a PTFE membrane. A linear response range was observed between 0.25 and 1.00mmol l-1 of oxalic acid; the data was fit by the equation A=-0.8(±1.5)+ 57.2(±2.5)[oxalate], with a correlation coefficient of 0.9971 and a relative standard deviation of 2% for n=5. The variance for a 0.25 mmol l-1 oxalic acid standard solution was lower than 4% for 11 measurements. The FIA system allows analysis of 20 samples per hour without prior treatment. The proposed method showed a good correlation with that of the Sigma Kit.

Fuel consumption of road commercial vehicles in the driving schedule

The fuel consumption is an important factor in the vehicle development due the fact that it has a direct effect on its trade aims. Besides that, it is known that the petrol is a scarce fuel. In this paper it is presented a procedure of fuel consumption calculation for a vehicle traveling in driving schedule. In such calculation it has been taken into account the operational conditions (load, pavement, climbing road, among others) and the building characteristics (map engine, transmission, frontal area, tire, among others) of road vehicles. There has also been an application of the theoretical model developed in a sample Mercedes-Benz do Brasil vehicle which has been compared with the values of experimental tests. Copyright © 1997 Society of Automotive Engineers, Inc.

Determination of metal ions in fuel ethanol after preconcentration on 5-amino-1,3,4-thiadiazole-2-thiol modified silica gel

This work describes the synthesis and characterization of 5-amino-1,3,4-thiadiazole-2-thiol modified silica gel (SiATT), and the results of a study of the adsorption and preconcentration (in batch, and in flow using a column technique) of Cd(II), Co(II), Cu(II), Fe(III), Ni(II), Pb(II) and Zn(II) in ethanol medium. The adsorption capacities for each metal ion were (in mmol g -1): Cd(II) = 0.11, Co(II) = 0.10, Cu(II) = 0.20, Fe(III) = 0.20, Ni(II) = 0.16, Pb(II) = 0.08 and Zn(II) = 0.12. The results obtained in the flow experiments, showed a recovery of ca. 100% of the metal ions adsorbed in a column packed with 2 g of SiATT, using 5 mL of 2.0 mol L -1 HCl solution as eluent. The sorption-desorption of the metal ions made possible the development of a preconcentration method and quantification by Flame AAS of metal ions at trace level in fuel ethanol.

Study of a fuel cell cogeneration system applied to a Brazilian tertiary sector

In this paper, a methodology for the study of a molten carbonate fuel cell cogeneration system and applied to a computer center building is developed. This system permits the recovery of waste heat, available between 600°C and 700°C, which can be used to the production of steam, hot and cold water, hot and cold air, depending on the recuperation equipment associated. Initially, some technical information about the most diffusing types of the fuel cell demonstration in the world are presented. In conclusion, the fuel cell cogeneration system may have an excellent opportunity to strengthen the decentralized energy production in the Brazilian tertiary sector.

Immobilization of lipases and assay in continuous fixed bed reactor

Lipases are versatile enzymes regarding the range of reactions they catalyse and substrates on which they act. They are as well important as catalyst in organic synthesis. Their immobilization on appropriate supports confer them greater stability besides the possibility of operating in continuous reactors. In order to explore these abilities, the reactions involving hydrolysis of p-nitrophenyl acetate (PNPA) and transesterification of PNPA with n-butanol were chosen. Lipases from two different sources were assayed, namely: microbial (Candida rugosa, CRL, Sigma Type VII) and pancreatic (PPL, Sigma, Type 11). Two immobilization methods were also used, namely: 1) adsorption, using as support the following silica derivatives (150-300μm e 450μ): phenyl, epoxy, amino and without derivation, and 2) covalent binding, using glutaraldehyde as binding agent and silica amino as support. This later method led to better results. Hydrolytic activity was 6.1 U/gsupport for CRL and 0.97U/gsupport for PPL, and of transesterification, 2,8U/gsupport for CRL and 1,9U/gsupport for PPL. Stability of the immobilized enzyme as a function of temperature was evaluated for CRL at 40°C and 50°C and for PPL at 32°C and 40°C. The assays were initially carried out batchwise, both for soluble and immobilized enzymes, aiming to the obtention of parameters for the continues reactor. Lipases immobilized by covalent binding were used in the assays of operacional stability in continuos reactors. For PPL in aqueous medium, at 32°C, and CRL in organic medium at 40°C, both operating continuously, no significant loss of activity was detected along the analysis period of 17 days. In the case of CRL in aqueous medium at 40°C there was a loss of activity around 40% after 18 days. For PPL in organic medium at 40°C the loss was 33% after 20 days. Compairing both sources with each other, very different results were obtained. Higher activitiy was found for CRL, both for hydrolysis and for transesterification reactions, with higher stability in organic medium. PPL showed lower activity as well as higher stability in aqueous medium. The immobilization method by covalent binding showed to be the most appropriate. Immobilized lipases are therefore relatively stable both in aqueous and organic medium.

Study of a hybrid solid oxide fuel cell: Energetic analysis and sankey diagram

In this paper a hybrid solid oxide fuel cell (SOFC) system is analyzed. This system applies a combined cycle utilizing gas turbine associated to a SOFC for rational decentralized energy production. Initially the relative concepts about the fuel cell are presented, followed by some chemical and technical informations such as the change of Gibbs free energy in isothermal fuel oxidation (or combustion) directly into electricity. This represents a very high fraction of the lower heating value (LHV) of a hydrocarbon fuel. In the next step a methodology for the study of SOFC associated with a gas turbine system is developed, considering the electricity and steam production for a hospital, as regard to the Brazilian conditions. This methodology is applied to energetic analysis. Natural gas is considered as a fuel. In conclusion, it is shown by a Sankey Diagram that the hybrid SOFC system may be an excellent opportunity to strengthen the decentralized energy production in Brazil. It is necessary to consider that the cogeneration in this version also is a sensible alternative from the technical point of view, demanding special methods of design, equipment selection and mainly of the contractual deals associated to electricity and fuel supply.

Thermodynamic analysis of direct steam reforming of ethanol in molten carbonate fuel cell

Fuel cell as MCFC (molten carbonate fuel cell) operate at high temperatures, and due to this issue, cogeneration processes may be performed, sending heat for own process or other purposes as steam generation in an industry. The use of ethanol for this purpose is one of the best options because this is a renewable and less environmentally offensive fuel, and cheaper than oil-derived hydrocarbons (in the case of Brazil). In the same country, because of technical, environmental and economic advantages, the use of ethanol by steam reforming process have been the most investigated process. The objective of this study is to show a thermodynamic analysis of steam reforming of ethanol, to determine the best thermodynamic conditions where are produced the highest volumes of products, making possible a higher production of energy, that is, a most-efficient use of resources. To attain this objective, mass and energy balances are performed. Equilibrium constants and advance degrees are calculated to get the best thermodynamic conditions to attain higher reforming efficiency and, hence, higher electric efficiency, using the Nernst equation. The advance degree of reforming increases when the operation temperature also increases and when the operation pressure decreases. But at atmospheric pressure (1 atm), the advance degree tends to the stability in temperatures above 700°C, that is, the volume of supplemental production of reforming products is very small for the high use of energy resources necessary. Reactants and products of the steam-reforming of ethanol that weren't used may be used for the reforming. The use of non-used ethanol is also suggested for heating of reactants before reforming. The results show the behavior of MCFC. The current density, at same tension, is higher at 700°C than other studied temperatures as 600 and 650°C. This fact occurs due to smaller use of hydrogen at lower temperatures that varies between 46.8 and 58.9% in temperatures between 600 and 700°C. The higher calculated current density is 280 mA/cm 2. The power density increases when the volume of ethanol to be used also increases due to higher production of hydrogen. The highest produced power at 190 mW/cm 2 is 99.8, 109.8 and 113.7 mW/cm2 for 873, 923 and 973K, respectively. The thermodynamic efficiency has the objective to show the connection among operational conditions and energetic factors, which are some parameters that describes a process of internal steam reforming of ethanol.

A preliminary physicochemical, exergetic and economic study of hydrogen production utilizing glycerol

This work has as objective to demonstrate technical and economic viability of hydrogen production utilizing glycerol. The volume of this substance, which was initially produced by synthetic ways (from oil-derived products), has increased dramatically due mainly to biodiesel production through transesterification process which has glycerol as main residue. The surplus amount of glycerol has been generally utilized to feed poultry or as fuel in boilers, beyond other applications such as production of soaps, chemical products for food industry, explosives, and others. The difficulty to allocate this additional amount of glycerol has become it in an enormous environment problem, in contrary to the objective of biodiesel chain, which is to diminish environmental impact substituting oil and its derivatives, which release more emissions than biofuels, do not contribute to CO2-cycle and are not renewable sources. Beyond to utilize glycerol in combustion processes, this material could be utilized for hydrogen production. However, a small quantity of works (theoretical and experimental) and reports concerning this theme could be encountered. Firstly, the produced glycerol must be purified since non-reacted amounts of materials, inclusively catalysts, contribute to deactivate catalysts utilized in hydrogen production processes. The volume of non-reacted reactants and non-utilized catalysts during transesterification process could be reutilized. Various technologies of thermochemical generation of hydrogen that utilizes glycerol (and other fuels) were evaluated and the greatest performances and their conditions are encountered as soon as the most efficient technology of hydrogen production. Firstly, a physicochemical analysis must be performed. This step has as objective to evaluate the necessary amount of reactants to produce a determined volume of hydrogen and determine thermodynamic conditions (such as temperature and pressure) where the major performances of hydrogen production could be encountered. The calculations are based on the process where advance degrees are found and hence, fractions of products (especially hydrogen, however, CO2, CO, CH4 and solid carbon could be also encountered) are calculated. To produce 1 Nm3/h of gaseous hydrogen (necessary for a PEMFC - Proton Exchange Membrane Fuel Cell - containing an electric efficiency of about 40%, to generate 1 kWh), 0,558 kg/h of glycerol is necessary in global steam reforming, 0,978 kg/h of glycerol in partial oxidation and cracking processes, and 0,782 kg/h of glycerol in autothermal reforming process. The dry reforming process could not be performed to produce hydrogen utilizing glycerol, in contrary to the utilization of methane, ethanol, and other hydrocarbons. In this study, steam reforming process was preferred due mainly to higher efficiencies of production and the need of minor amount of glycerol as cited above. In the global steam reforming of glycerine, for one mole of glycerol, three moles of water are necessary to produce three moles of CO2 and seven moles of H2. The response reactions process was utilized to predict steam reforming process more accurately. In this mean, the production of solid carbon, CO, and CH4, beyond CO2 and hydrogen was predicted. However, traces of acetaldehyde (C2H2), ethylene (C2H4), ethylene glycol, acetone, and others were encountered in some experimental studies. The rates of determined products obviously depend on the adopted catalysts (and its physical and chemical properties) and thermodynamic conditions of hydrogen production. Eight reactions of steam reforming and cracking were predicted considering only the determined products. In the case of steam reforming at 600°C, the advance degree of this reactor could attain its maximum value, i.e., overall volume of reactants could be obtained whether this reaction is maintained at 1 atm. As soon as temperature of this reaction increases the advance degree also increase, in contrary to the pressure, where advance degree decrease as soon as pressure increase. The fact of temperature of reforming is relatively small, lower costs of installation could be attained, especially cheaper thermocouples and smaller amount of thermo insulators and materials for its assembling. Utilizing the response reactions process in steam reforming, the predicted volumes of products, for the production of 1 Nm3/h of H2 and thermodynamic conditions as cited previously, were 0,264 kg/h of CO (13% of molar fraction of reaction products), 0,038 kg/h of CH4 (3% of molar fraction), 0,028 kg/h of C (3% of molar fraction), and 0,623 kg/h of CO2 (20% of molar fraction). Through process of water-gas shift reactions (WGSR) an additional amount of hydrogen could be produced utilizing mainly the volumes of produced CO and CH4. The overall results (steam reforming plus WGSR) could be similar to global steam reforming. An attention must to be taking into account due to the possibility to produce an additional amount of CH4 (through methanation process) and solid carbon (through Boudouard process). The production of solid carbon must to be avoided because this reactant diminishes (filling the pores) and even deactivate active area of catalysts. To avoid solid carbon production, an additional amount of water is suggested. This method could be also utilized to diminish the volume of CO (through WGSR process) since this product is prejudicial for the activity of low temperature fuel cells (such as PEMFC). In some works, more three or even six moles of water are suggested. A net energy balance of studied hydrogen production processes (at 1 atm only) was developed. In this balance, low heat value of reactant and products and utilized energy for the process (heat supply) were cited. In the case of steam reforming utilizing response reactions, global steam reforming, and cracking processes, the maximum net energy was detected at 700°C. Partial oxidation and autothermal reforming obtained negative net energy in all cited temperatures despite to be exothermic reactions. For global steam reforming, the major value was 114 kJ/h. In the case of steam reforming, the highest value of net energy was detected in this temperature (-170 kJ/h). The major values were detected in the cracking process (up to 2586 kJ/h). The exergetic analysis has as objective, associated with physicochemical analysis, to determine conditions where reactions could be performed at higher efficiencies with lower losses. This study was performed through calculations of exergetic and rational efficiencies, and irreversibilities. In this analysis, as in the previously performed physicochemical analysis, conditions such as temperature of 600°C and pressure of 1 atm for global steam reforming process were suggested due to lower irreversibility and higher efficiencies. Subsequently, higher irreversibilities and lower efficiencies were detected in autothermal reforming, partial oxidation and cracking process. Comparing global reaction of steam reforming with more-accurate steam reforming, it was verified that efficiencies were diminished and irreversibilities were increased. These results could be altered with introduction of WGSR process. An economic analysis could be performed to evaluate the cost of generated hydrogen and determine means to diminish the costs. This analysis suggests an annual period of operation between 5000-7000 hours, interest rates of up to 20% per annum (considering Brazilian conditions), and pay-back of up to 20 years. Another considerations must to be take into account such as tariffs of utilized glycerol and electricity (to be utilized as heat source and (or) for own process as pumps, lamps, valves, and other devices), installation (estimated as US$ 15.000 for a plant of 1 Nm3/h) and maintenance cost. The adoption of emission trading schemes such as carbon credits could be performed since this is a process with potential of mitigates environment impact. Not considering credit carbons, the minor cost of calculated H2 was 0,16288 US$/kWh if glycerol is also utilized as heat sources and 0,17677 US$/kWh if electricity is utilized as heat sources. The range of considered tariff of glycerol was 0-0,1 US$/kWh (taking as basis LHV of H2) and the tariff of electricity is US$ 0,0867 US$/kWh, with demand cost of 12,49 US$/kW. The costs of electricity were obtained by Companhia Bandeirante, localized in São Paulo State. The differences among costs of hydrogen production utilizing glycerol and electricity as heat source was in a range between 0,3-5,8%. This technology in this moment is not mature. However, it allows the employment generation with the additional utilization of glycerol, especially with plants associated with biodiesel plants. The produced hydrogen and electricity could be utilized in own process, increasing its final performance.