20 resultados para Methane thiosulfonate
Resumo:
Density functional theory with gradient corrections has been employed to study the reaction pathways and the reaction energetics for the transformations of CH4 to C and H on a Pd(100) surface. On examination of transition state structures identified in each elementary reaction, a clear relationship between the valencies of the CHx fragments and the locations of the transition states emerges. The higher the valency of the CHx fragment, the higher the coordination number of the CHx with the surface atoms. The calculated reaction energetics are in good agreement with the experiments. In addition, calculation results are also used to illustrate an interesting issue concerning the CH3 stability on Pd surfaces. (C) 2002 American Institute of Physics.
Resumo:
The effect of SO2 on Pd-based catalysts for the combustion of methane has been investigated. It is shown that while SO2 poisons Al2O3- and SiO2-supported catalysts. pre-treatment of Pd/ZrO2 by SO2 enhances the activity substantially.
Resumo:
C21H22N6O8S2, monoclinic, P12(1)/n1 (no. 14), a = 10.1931(8) angstrom, b = 11.9627(7) angstrom, c = 20.299(2) angstrom, beta = 95.131(4)degrees, V = 2465.2 A(3), Z = 4, R-gt(F) = 0.079, wR(ref)(F-2) = 0.229, T = 100 K.
Resumo:
Experimental values for the solubility of carbon dioxide, ethane, methane, oxygen, nitrogen, hydrogen, argon and carbon monoxide in 1-butyl-3- methylimidazolium tetrafluoroborate, [bmim][BF4] - a room temperature ionic liquid - are reported as a function of temperature between 283 K and 343 K and at pressures close to atmospheric. Carbon dioxide is the most soluble gas with mole fraction solubilities of the order of 10-2. Ethane and methane are one order of magnitude more soluble than the other five gases that have mole fraction solubilities of the order of 10-4. Hydrogen is the less soluble of the gaseous solutes studied. From the variation of solubility, expressed as Henry's law constants, with temperature, the partial molar thermodynamic functions of solvation such as the standard Gibbs energy, the enthalpy, and the entropy are calculated. The precision of the experimental data, considered as the average absolute deviation of the Henry's law constants from appropriate smoothing equations is of 1%. © 2005 Elsevier Ltd. All rights reserved.
Resumo:
Methane activation via bromination can be a feasible route with selective synthesis of mono-bromomethane. It is known that the condensation of brominated products into higher hydrocarbons can result in coking and deactivation in the presence of di-bromomethane. In this study, selective production of methyl bromide was investigated over sulfated ZrO2 included SBA-15 structures. It was observed that the higher the ZrO2 amounts the higher the conversion, while the catalyst remained >99% selective for the monobrominated methane. Over 25 mol.% ZrO2 included SBA-15 catalyst with a BET surface area of 246 m(2)/g, methane was brominated with 69% conversion at 340 degrees C and only CH3Br was selectively produced. (C) 2009 Elsevier B.V. All rights reserved
Resumo:
Activation of methane with a halogen followed by the metathesis of methyl halide is a novel route from methane to higher hydrocarbons or oxygenates. Thermodynamic analysis revealed that bromine is the most suitable halogen for this goal. Analysis of the published data on the reaction kinetics in a CSTR enabled us to judge on the effects of temperature, reactor residence time and the feed concentrations of bromine and methane to the conversion of methane and the selectivity towards mono or dibromomethane. The analysis indicated that high dibromomethane selectivity is attainable (over 90%) accompanied by high methane conversions. The metathesis of dibromomethane can provide an alternative route to the conversion of methane (natural gas) economically with smaller installations than the current syn-gas route. (c) 2005 Elsevier B.V. All rights reserved.
Resumo:
Ni/K-MgO-ZrO catalysts for dry reforming of methane, with a range of Mg/Zr ratios and each containing about 10 wt% Ni, were prepared via Ni nitrate impregnation on MgO-ZrO supports synthesized by co-precipitation using KCO. It was found that a proportion of the potassium of the precipitant remained in the samples and improved the stability of the catalysts in the reaction. It was also shown that reduction of the catalysts at 1,023 K without calcination in air is necessary for stable and high activity; calcination in air at 1,073 K gives a deterioration of the catalytic properties, leading to rapid deactivation during the reaction. The order of the CH conversions of the reduced catalysts after 14 h on stream was as follows: Ni/K-MgZr ~ Ni/K-Mg ≥ Ni/K-MgZr Ni/K-Zr. A catalyst with 0.95 wt% K on MgO-ZrO with a Mg:Zr mole ratio of 5:2 showed the best resistance to deactivation. Experiments in a microbalance system showed that there was only negligible coke deposition on the surface of this sample. This behaviour was attributed to the presence of Ni nanoparticles with a diameter of less than 10 nm located on a MgO/NiO solid solution shell doped by K ions; this in turn covers a core of tetragonal ZrO and/or a MgO/ZrO solid solution. This conclusion was supported by EDS/TEM, XPS, XRD and H chemisorption measurements. © 2013 Springer Science+Business Media New York.
Resumo:
Gas-to-liquid processes are generally used to convert natural gas or other gaseous hydrocarbons into liquid fuels via an intermediate syngas stream. This includes the production of liquid fuels from biomass-derived sources such as biogas. For example, the dry reforming of methane is done by reacting CH4 and CO2, the two main components of natural biogas, into more valuable products, i.e., CO and H2. Nickel containing perovskite type catalysts can promote this reaction, yielding good conversions and selectivities; however, they are prone to coke laydown under certain operating conditions. We investigated the addition of high oxygen mobility dopants such as CeO2, ZrO2, or YSZ to reduce carbon laydown, particularly using reaction conditions that normally result in rapid coking. While doping with YSZ, YDC, GDC, and SDC did not result in any improvement, we show that a Ni perovskite catalyst (Na0.5La0.5Ni0.3Al0.7O2.5) doped with 80.9 ZrO2 15.2 CeO2 gave the lowest amount of carbon formation at 800 °C and activity was maintained over the operating time.
Resumo:
A low temperature, isothermal, gas-phase, recyclable process is described for the partial oxidation of methane to methanol over Cu–ZSM-5. Activation in NO at 150 °C followed by methane reaction and steam extraction (both at 150 °C) allowed direct observation of methanol at the reactor outlet.
Resumo:
Soil gas emissions of methane and carbon dioxide on brownfield sites are usually attributed to anthropogenic activities; however geogenic sources of soil gas are often not considered during site investigation and risk management strategies. This paper presents a field study at a redeveloped brownfield site on a flood plain to identify accumulations of methane biogas trapped in underlying sediments. The investigation is based on a multidisciplinary approach using direct multi-level sampling measurements and Earth resistivity tomography . Resistivity imaging was applied to evaluate the feasibility of identifying the size and spatial continuity of soil gas accumulations in anthropogenic and naturally occurring deposits. As a result, biogas accumulations are described within both anthropogenic deposits and pristine organic sediments. This result is important to identify the correct approaches to identify and manage risks associated with soil gas emissions on brownfield and pristine sites. The organic-rich sediments in Quaternary fluvial environments of São Paulo Basin in particular the Tietê River, biogas reservoirs can be generated and trapped beneath geogenic and anthropogenic layers, potentially requiring the management of brownfield developments across this region.
Resumo:
The methane solubility in five pure electrolyte solvents and one binary solvent mixture for lithium ion batteries – such as ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC) and the (50:50 wt%) mixture of EC:DMC was studied experimentally at pressures close to atmospheric and as a function of temperature between (280 and 343) K by using an isochoric saturation technique. The effect of the selected anions of a lithium salt LiX (X = hexafluorophosphate,
<img height="16" border="0" style="vertical-align:bottom" width="27" alt="View the MathML source" title="View the MathML source" src="http://origin-ars.els-cdn.com/content/image/1-s2.0-S0021961414002146-si1.gif">PF6-; tris(pentafluoroethane)trifluorurophosphate, FAP−; bis(trifluoromethylsulfonyl)imide, TFSI−) on the methane solubility in electrolytes for lithium ion batteries was then investigated using a model electrolyte based on the binary mixture of EC:DMC (50:50 wt%) + 1 mol · dm−3 of lithium salt in the same temperature and pressure ranges. Based on experimental solubility data, the Henry’s law constant of the methane in these solutions were then deduced and compared together and with those predicted by using COSMO-RS methodology within COSMOthermX software. From this study, it appears that the methane solubility in each pure solvent decreases with the temperature and increases in the following order: EC < PC < EC:EMC (50:50 wt%) < DMC < EMC < DEC, showing that this increases with the van der Walls force in solution. Additionally, in all investigated EC:DMC (50:50 wt%) + 1 mol · dm−3 of lithium salt electrolytes, the methane solubility decreases also with the temperature and the methane solubility is higher in the electrolyte containing the LiFAP salt, followed by that based on the LiTFSI one. From the variation of the Henry’s law constants with the temperature, the partial molar thermodynamic functions of solvation, such as the standard Gibbs free energy, the enthalpy, and the entropy where then calculated, as well as the mixing enthalpy of the solvent with methane in its hypothetical liquid state. Finally, the effect of the gas structure on their solubility in selected solutions was discussed by comparing methane solubility data reported in the present work with carbon dioxide solubility data available in the same solvents or mixtures to discern the more harmful gas generated during the degradation of the electrolyte, which limits the battery lifetime.