935 resultados para Steam reforming of methanol
Resumo:
Pt-modified RuO2 was prepared by a sol-gel procedure on titanium substrates in the form of thin films of similar to2-mum thickness. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analyses showed that these films actually consist of Pt nanoparticles dispersed in RuO2 and that neither metallic Ru nor Pt-Ru alloy are present on the surface. Electrodes with different Pt:Ru nominal compositions were prepared and their electrocatalytic activity for the oxidation of methanol was investigated by potential sweeps and chronoamperometry. The results obtained show an enhancement effect for methanol oxidation that can be interpreted as associated to the formation of hydrous oxides on the RuO2 surface.
Resumo:
The CO2 reforming of CH4 was carried out over Ni catalysts supported on γ-Al2O3 and CeO 2-promoted γ-Al2O3. The catalysts were characterized by means of surface area measurements, TPR, CO2 and H2 chemisorption, XRD, SEM, and TEM. The CeO2 addition promoted an increase of catalytic activity and stability. The improvement in the resistance to carbon deposition is attributed to the highest CO2 adsorption presented by the CeO2 addition. The catalytic behavior presented by the samples, with a different CH4/CO2 ratio used, points to the CH4 decomposition reaction as the main source of carbon deposition.
Resumo:
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.
Resumo:
The paper presents a process of cellulose thermal degradation with bio-hydrogen generation and zinc nanostructures synthesis. Production of zinc nanowires and zinc nanoflowers was performed by a novel processes based on cellulose pyrolysis, volatiles reforming and direct reduction of ZnO. The bio-hydrogen generated in situ promoted the ZnO reduction with Zn nanostructures formation by vapor–solid (VS) route. The cellulose and cellulose/ZnO samples were characterized by thermal analyses (TG/DTG/DTA) and the gases evolved were analyzed by FTIR spectroscopy (TG/FTIR). The hydrogen was detected by TPR (Temperature Programmed Reaction) tests. The results showed that in the presence of ZnO the cellulose thermal degradation produced larger amounts of H2 when compared to pure cellulose. The process was also carried out in a tubular furnace with N2 atmosphere, at temperatures up to 900 °C, and different heating rates. The nanostructures growth was catalyst-free, without pressure reduction, at temperatures lower than those required in the carbothermal reduction of ZnO with fossil carbon. The nanostructures were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS) and transmission electron microscopy (TEM). The optical properties were investigated by photoluminescence (PL). One mechanism was presented in an attempt to explain the synthesis of zinc nanostructures that are crystalline, were obtained without significant re-oxidation and whose morphologies are dependent on the heating rates of the process. This route presents a potential use as an industrial process taking into account the simple operational conditions, the low costs of cellulose and the importance of bio-hydrogen and nanostructured zinc.
Resumo:
As in the case of most small organic molecules, the electro-oxidation of methanol to CO2 is believed to proceed through a so-called dual pathway mechanism. The direct pathway proceeds via reactive intermediates such as formaldehyde or formic acid, whereas the indirect pathway occurs in parallel, and proceeds via the formation of adsorbed carbon monoxide (COad). Despite the extensive literature on the electro-oxidation of methanol, no study to date distinguished the production of CO2 from direct and indirect pathways. Working under, far-from-equilibrium, oscillatory conditions, we were able to decouple, for the first time, the direct and indirect pathways that lead to CO2 during the oscillatory electro-oxidation of methanol on platinum. The CO2 production was followed by differential electrochemical mass spectrometry and the individual contributions of parallel pathways were identified by a combination of experiments and numerical simulations. We believe that our report opens some perspectives, particularly as a methodology to be used to identify the role played by surface modifiers in the relative weight of both pathways-a key issue to the effective development of catalysts for low temperature fuel cells.
Resumo:
One of the key objectives in fuel cell technology is to reduce Pt loading by the improvement of its catalytic activity towards alcohol oxidation. Here, a sol-gel based method was used to prepare ternary and quaternary carbon supported nanoparticles by combining Pt-Ru with Mo, Ta, Pb, Rh or Ir, which were used as electro-catalysts for the methanol and ethanol oxidation reactions in acid medium. Structural characterization performed by XRD measurements revealed that crystalline structures with crystallites ranging from 2.8 to 4.1 nm in size and with different alloy degrees were produced. Tantalum and lead deposited as a heterogeneous mixture of oxides with different valences resulting in materials with complex structures. The catalysts activities were evaluated by cyclic voltammetry and by Tafel plots and the results showed that the activity towards methanol oxidation was highly dependent of the alloy degree, while for ethanol the presence of a metal capable to promote the break of C-C bond, such as Rh, was necessary for a good performance. Additionally, the catalysts containing of TaOx or PbOx resulted in the best materials due to different effects: the hi-functional mechanism promoted by TaOx and a better dispersion of the catalysts constituents promoted by PbOx. (C) 2012 Elsevier B.V. All rights reserved.
Resumo:
Ni catalysts supported on gamma-Al2O3 modified by Rh and La were prepared and evaluated on the reforming of a model biogas. The catalysts were characterized by EDS, XRD, TPR, XANES and surface area estimation (BET). The results showed that in the original Ni catalyst, the Ni interacted strongly with the alumina support, exhibiting high reduction temperatures in TPR tests. In the catalytic tests, the addition of Rh on Ni catalysts improved CH4 conversion but also increased carbon deposition, possible by causing the segregation of Ni species under the reaction conditions. The presence of La on Ni catalysts reduced the carbon deposition by favoring the gasification of carbon species. Addition of synthetic air to the process improved the CH4 conversion and also decreased the carbon formation. The catalysts Ni, Rh-NiLa, and Rh showed good results in the conversion of model sulfur-free biogas, which suggests that they are promising catalysts to be tested in conversion of real biogas. (C) 2012 Elsevier B.V. All rights reserved.
Resumo:
A low-cost chemiresistive gas sensor is described, made by the deposition of a thin film of a conductive polymer, poly(2-dodecanoylsulfanyl-p-phenylenevinylene), doped with dodecylbenzenesulfonic acid (10%, w/w), onto interdigitated electrodes. The sensor exhibits linear electrical conductance changes in function of the concentration of methanol present in sugar-cane spirit in the range between 0.05% and 4.0%. Since the sensor is cheap, easy to fabricate, durable, presents low power consumption, and is not sensitive to ethanol, acetic acid or water, it can be used in portable equipments for monitoring methanol levels in distilled alcoholic beverages such as Brazilian sugar-cane spirit (cachaca). (C) 2011 Elsevier Ltd. All rights reserved.
Resumo:
L'idrogeno è un prodotto di grande importanza per l'industria chimica ed i processi di raffineria. Il 60% dell'intera produzione di idrogeno viene dal reforming del gas naturale. L'oxy-reforming è un processo che unisce la reazione di steam reforming a quella di ossidazione parziale e che ha dimostrato di avere molti vantaggi in termini di temperature molto più basse, minor volume di vapore alimentato con conseguente minori costi energetici e tempi di contatto sul catalizzatore. Per questo processo sono stati preparati, testati e caratterizzati catalizzatori a base di ossidi misti Ce-Zr impregnati con Rh. Particolare attenzione è stata posta all'effetto sulle prestazioni catalitiche del metodo di sintesi e della natura della fase costituente il supporto. Sperimentalmente è stato osservato che il catalizzatore il cui supporto è stato ottenuto via microemulsione ha una migliore attività rispetto al coprecipitato e che la fase ottimale corrisponde ad un rapporto Ce-Zr 0,5-0,5.
Resumo:
Mechanistic investigations on the previously reported reduction of B-alkylcatecholboranes in the presence of methanol led to the disclosure of a new mechanism involving catechol as a reducing agent. More than just revising the mechanism of this reaction, we disclose here the surprising role of catechol, a chain breaking antioxidant, which becomes a source of hydrogen atoms in an efficient radical chain process
Resumo:
The intent of this research was to identify the level of risk methanol posed to a fetus during an ethanol co-exposure. This investigation was prompted by the known competitive inhibition properties of ethanol and the developmental toxicity of methanol. Integrated into this research was the practicality necessitated by regulatory processes, namely: does the risk justify the expense of additional research. To this end, the scope and nature of exposures were summarized to illustrate the ubiquity of these chemicals and the potential for dual exposure. Similarly, severity of outcome was evaluated by systematically reviewing the LOAELs, NOAELs, and statistical significance contained in methanol-induced developmental studies. Results. Blood methanol levels corresponding to developmental effects in laboratory studies were found to be substantially higher than the blood methanol levels predicted in high-risk methanol-ethanol exposure scenarios. This indicates that ethanol would not likely exacerbate methanol toxicity to the point of teratogenicity; however, it is important to note that the developmental toxicity of ethanol—an established human teratogen—was not included in the evaluation. Ethanol's contribution as a developmental toxicant rather than merely as an attenuator of methanol toxicity undermines the severity of effects possible from this chemical combination. Therefore further evaluation is needed to assess the developmental toxicities following dual exposures before rendering methanol and ethanol a high-priority mixture.^
Resumo:
Sewage sludge gasification assays were performed in an atmospheric fluidised bed reactor using air and air–steam mixtures as the gasifying agents. Dolomite, olivine and alumina are three well known tar removal catalysts used in biomass gasification processing. However, little information is available regarding their performance in sewage sludge gasification. The aim of the current study was to learn about the influence of these three catalysts in the product distribution and tar production during sewage sludge gasification. To this end, a set of assays was performed in which the temperature (750–850 °C), the in-bed catalyst content (0, 10 and 15 wt.%) and the steam–biomass ratio (SB) in the range of 0–1 were varied with a constant equivalence ratio (ER) of 0.3. The results were compared to the results from gasification without a catalyst. We show that dolomite has the highest activity in tar elimination, followed by alumina and olivine. In addition to improving tar removal, the presence of water vapour and the catalysts increased the content of H2 in the gases by nearly 60%.
Resumo:
Numerous references can be found in scientific literature regarding biomass gasification. However, there are few works related to sludge gasification. A study of sewage sludge gasification process in a bubbling fluidised bed gasifier on a laboratory scale is here reported. The aim was to find the optimum conditions for reducing the production of tars and gain more information on the influx of different operating variables in the products resulting from the gasification of this waste. The variables studied were the equivalence ratio (ER), the steam-biomass ratio (SB) and temperature. Specifically, the ER was varied from 0.2 to 0.4, the SB from 0 to 1 and the temperature from 750 °C (1023 K) to 850 °C (1123 K). Although it was observed that tar production could be considerably reduced (up to 72%) by optimising the gasification conditions, the effect of using alumina (aluminium oxide, of proven efficacy in destroying the tar produced in biomass gasification) as primary catalyst in air and air-steam mixture tests was also verified. The results show that by adding small quantities of alumina to the bed (10% by weight of fed sludge) considerable reductions in tar production can be obtained (up to 42%) improving, at the same time, the lower heating value (LHV) of the gas and carbon conversion.