Activity surfaces, methanation

Here n indicates an active surface site, and X— indicates die species X adsorbed on an active site. The first reaction allows for the possibility that methane may occupy more than one active site on adsorption. The dik d and fourth reactions show die observed retarding effects of steam and hydrogen... 

The role of oxygen and hydrogen solutions in the metal catalyst does not appear to be that of impeding the major reactions, but merely to provide a source of these reactants which is uniformly distributed diroughout the catalyst particles, without decreasing die number of surface sites available to methane adsorption. It is drerefore quite possible that a significatit fraction of the reaction takes place by the formation of products between species adsorbed on the surface, and dissolved atoms just below the surface, but in adjacent sites to the active surface sites. 

The trend is illustrated for ammonia activation in Figure 1.17 [19]. In this figure, the activation energies of ammonia activation are compared for stepped and nonstepped surfaces of Pt. Similarly as also found for H2O activation [20], the dissociation barrier is found to be invariant to surface structural changes. This is very different compared to the earlier discussed activation of methane that shows a very strong structural dependence. 

Oxygen-containing molecules cannot be tolerated in the ammonia synthesis, primarily because they form iron oxide that blocks the active surface. First the CO2 is removed, through a scrubber, by reaction with a strong base. The remaining CO (and CO2) is then removed by the methanation reaction, converting the CO into methane and water. Finally the water is removed by, for example, molecular sieves. Methane does not present problems because it interacts weakly with the catalyst surface. The gas mixture (Tab. 8.6) is compressed to the roughly 200 bar needed for ammonia synthesis and admitted to the reactor. 

Fig.l Surface area and catalytic activity for methane combustion of AMnAlii-Oi9methane conversion level is 10%. Reaction condition CH4,1 vol% air, 99 vol% space velocity, 48 OOOh ... 

CP/MAS NMR study of CH4 activation on [(=SiO)2Ta(H)J shows the formation even at 150 °C of methyUdene and methyUdyne species by an a-H elimination process on several sites that should correspond to the tris-hydride on other sites a methyl group is transferred to the surface, leading to the formation of (=Si-Me) and of [(=SiO)3Ta]. Correlation with EXAFS suggests that the tris-hydride should exist on surface sites (=20%) quite distant from siloxy bridges whereas methyl transfer to the surface should happen on the specific sites (=80%) close to the siloxy bridges. The latter, which are formally 10 electrons species, exhibit a moderate to weak activity in methane C-H activation. To the best of our knowledge, this is the first observation of methyl group transfer on a surface (Scheme 2.18). 

Two series of catalysts were synthesized for subsequent evaluation as methane dimerization catalysts. The first series was alkali modified zinc oxide (6) and magnesium oxide catalysts (7), which were reported to be active for methane activation, while the second series was ion modified perovskites described by Machida and Enyo (8). The objective of the present study was to determine whether the aerosol technique could provide a wide range of ion substitutions as homogeneous solid solutions, and to determine whether moderately high surface area catalysts could... 

Ni-Pd. Moss et al. (252) reported that 60% Pd (in bulk) catalysts (i.e., those which have almost 100% Pd in the surface) had almost the same activity in ethane hydrogenolysis as pure Ni, although pure Pd itself is not very active. This might be an indication that for this reaction mixed ensembles of Pd-Ni can operate. In this respect it is interesting that Driessen recently found that in contrast to this, a 75% Pd (bulk) catalyst [the exchange reaction detected (255) the presence of some Ni in the surface of a catalyst of this composition] showed no activity in methanation, compared to Ni. 

We conclude, therefore, that the mechanisms of catalytic cracking reactions on nickel metal and nickel carbide are closely comparable, but that the latter process is subject to an additional constraint, since a mechanism is required for the removal of deposited carbon from the active surfaces of the catalyst. Two phases are present during reactions on the carbide, the relative proportions of which may be influenced by the composition of the gaseous reactant present, but it is not known whether the contribution from reactions on the carbide phase is appreciable. Since reactions involving nickel carbide yielded products other than methane, surface processes involved intermediates other than those mentioned in Scheme I, although there is also the possibility that if cracking reactions were confined to the metal present, entirely different chemical changes may proceed on the surface of nickel carbide. 

The biologically active surface (to 10 cm depth) has a methane flux that varies between 1 and 100 mmC/m2 per day. The hydrate results from free gas and gas dissolved in water. Two types of hydrate fabric result (1) porous hydrates, from accumulation of bubbles of free gas and (2) massive hydrates, with twice the density of porous hydrates (0.9 g/L versus 0.4 g/L). In the recent Raman spectroscopy, southern Hydrate Ridge experiments by the MBARI (Hester et al., 2005), the near-surface hydrate Raman specta contained significant amounts of free gas as well as hydrates, with only a trace of hydrogen sulfide in the methane gas. 

The principal methods of gas activation are thermal and electrical much less common are chemical and photochemical activation. In the most commonly used thermal activation technique - the hot filament technique - a W or Ta wire is arranged in the immediate vicinity of the substrate to be coated by diamond (Fig. 1). The wire is heated until it reaches the temperature when H2 molecules dissociate readily. The gas phase is a mixture of a carbon-containing gas (e.g. methane, acetone or methanol vapor), at a concentration of a few per cent, and hydrogen. Upon the contact of the gas with the activator surface, excited carbon-containing molecules and radicals are produced, in addition to the hydrogen atoms. They are transferred to the substrate surface, where deposition occurs. Table 2 gives an indication of the hot-filament deposition process parameters. 

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