Methane, steam reforming case

The extent to which anode polarization affects the catalytic properties of the Ni surface for the methane-steam reforming reaction via NEMCA is of considerable practical interest. In a recent investigation62 a 70 wt% Ni-YSZ cermet was used at temperatures 800° to 900°C with low steam to methane ratios, i.e., 0.2 to 0.35. At 900°C the anode characteristics were i<>=0.2 mA/cm2, Oa=2 and ac=1.5. Under these conditions spontaneously generated currents were of the order of 60 mA/cm2 and catalyst overpotentials were as high as 250 mV. It was found that the rate of CH4 consumption due to the reforming reaction increases with increasing catalyst potential, i.e., the reaction exhibits overall electrophobic NEMCA behaviour with a 0.13. Measured A and p values were of the order of 12 and 2 respectively.62 These results show that NEMCA can play an important role in anode performance even when the anode-solid electrolyte interface is non-polarizable (high Io values) as is the case in fuel cell applications. 

M REC, as the TREC, does not depend on the reaction path. In addition, there is no dependence on the membrane-permeation properties (related to the time required for species permeation).1 In any case, the final value reached depends on the extractive capacity of the system, for example, the pressure and composition on the permeate side. The composition on the permeate side, similarly to the feed molar ratio, can be expressed by considering the ratio (named sweep factor) between the initial molar number of nonpermeating species (present on the permeate side) and the initial molar number of the reference reactant, for example, methane for methane steam reforming, or carbon monoxide for water gas shift). The sweep factor was defined for a closed M Ras ... 

All these factors are functions of the concentration of the chemical species, temperature and pressure of the system. At constant diffu-sionai resistance, the increase in the rate of chemical reaction decreases the effectiveness factor while al a constant intrinsic rate of reaction, the increase of the diffusional resistances decreases the effectiveness factor. Elnashaie et al. (1989a) showed that the effect of the diffusional resistances and the intrinsic rate of reactions are not sufficient to explain the behaviour of the effectiveness factor for reversible reactions and that the effect of the equilibrium constant should be introduced. They found that the effectiveness factor increases with the increase of the equilibrium constants and hence the behaviour of the effectiveness factor should be explained by the interaction of the effective diffusivities, intrinsic rates of reaction as well as the equilibrium constants. The equations of the dusty gas model for the steam reforming of methane in the porous catalyst pellet, are solved accurately using the global orthogonal collocation technique given in Appendix B. Kinetics and other physico-chemical parameters for the steam reforming case are summarized in Appendix A. 

The application of membrane reactors to methane reforming has also been evaluated in two recent studies. A technical and economic evaluation of the use of dense Pd-membrane in methane steam reforming has been presented by Aasberg-Petersen et aL [6.10]. They assumed a thin (2 Lim thick) Pd membrane, which exhibited perfect separation and, as a result, the pure hydrogen product was taken from the permeate side of the membrane. No sweep gas was used on the permeate side of the reactor. This necessitated compression of the low pressure hydrogen product. The authors concluded that membrane-based reforming using a dense film membrane became attractive only in the cases where electrical costs were low. 

Increasing the HRF leads to higher hydrogen production (from 380 to 570 MW), as well as membrane surface area (from 8600 to 11 000 m ) the former is predominant, since specific costs decrease significantly, as shown in Table 14.13, from 45% to 55% of HRF. For all HRF, this solution has a lower amount of hydrogen produced than reference case with methane steam reforming. 

Find et al. [25] developed a nickel-based catalyst for methane steam reforming. As material for the microstructured plates, AluchromY steel, which is an FeCrAl alloy, was applied. This alloy forms a thin layer of alumina on its surface, which is less than 1 tm thick. This layer was used as an adhesion interface for the catalyst, a method which is also used in automotive exhaust systems based on metallic monoliths. Its formation was achieved by thermal treatment of microstructured plates for 4h at 1000 °C. The catalyst itself was based on a nickel spinel (NiAl204), which stabUizes the catalyst structure. The sol-gel technique was then used to coat the plates with the catalyst slurry. Good catalyst adhesion was proven by mechanical stress and thermal shock tests. Catalyst testing was performed in packed beds at a S/C ratio of 3 and reaction temperatures between 527 and 750 °C. The feed was composed of 12.5 vol.% methane and 37.5 vol.% steam balance argon. At a reaction temperature of 700°C and 32 h space velocity, conversion dose to the thermodynamic equilibrium could be achieved. During 96 h of operation the catalyst showed no detectable deactivation, which was not the case for a commercial nickel catalyst serving as a base for comparison. 

Figure 1.9 shows the conversions in the methane steam reforming and shift reactions, if they are treated as independent reactions. The conversion in the endothermic steam reforming is increasing with temperature, whereas the opposite is the case for the shift reaction. 

Simulations by Barbieri and Di Maio [411] and experimental work performed by Lin et al. [416] showed the opposite trend for the case of methane steam reforming under non-ideal conditions. With a palladium membrane of 20-25 pm thickness, which showed infinite selectivity for hydrogen separation, decreased methane conversion was obtained with increased reaction pressure [416]. 

Steam Reforming Processes. In the steam reforming process, light hydrocarbon feedstocks (qv), such as natural gas, Hquefied petroleum gas, and naphtha, or in some cases heavier distillate oils are purified of sulfur compounds (see Sulfurremoval and recovery). These then react with steam in the presence of a nickel-containing catalyst to produce a mixture of hydrogen, methane, and carbon oxides. Essentially total decomposition of compounds containing more than one carbon atom per molecule is obtained (see Ammonia Hydrogen Petroleum). 

The principle of Le Chatelier shows that when the pressure applied to a gaseous system is increased, dre equilibrium composition will chairge in order to reduce tire number of gaseous molecules. In the case of tire steam reforming of metlrane, the partial pressures of methane and steam will increase as the pressure is increased. In the water-gas reaction, where tire number of molecules is the same on both sides of the equation, the effect of increasing... 

Direct thermal decomposition of methane was carried out, using a thermal plasma system which is an environmentally favorable process. For comparison, thermodynamic equilibrium compositions were calculated by software program for the steam reforming and thermal decomposition. In case of thermal decomposition, high purity of the hydrogen and solidified carbon can be achieved without any contaminant. 

Both of these reactions are exothermic and are favoured by reduction in temperature. Hence, while the products of the steam reforming reaction at higher temperatures ( 800 °C) are CO and H2, lower temperatures are used to produce methane-rich gases in this case, the overall reaction can be approximated by ... 

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