A review of the effect of the addition of hydrogen in the selective catalytic reduction of NOx with hydrocarbons on silver catalysts

Research is progressing fast in the field of the hydrogen assisted hydrocarbon selective catalytic reduction (HC-SCR) over Ag-based catalysts: this paper is a review of the work to date in this area. The addition of hydrogen to the HC-SCR reaction feed over Ag/Al2O3 results in a remarkable improvement in NO (x) conversion using a variety of different hydrocarbon feeds. There is some debate concerning the role that hydrogen has to play in the reaction mechanism and its effect on the form of Ag present during the reaction. Many of the studies use in situ UV-Vis spectroscopy to monitor the form of Ag in the catalyst and appear to indicate that the addition of hydrogen promotes the formation of small Ag clusters which are highly reactive for NO (x) conversion. However, some authors have expressed concern about the use of this technique for these materials and further work is required to address these issues before this technique can be used to give an accurate assessment of the state of Ag during the SCR reaction. A study using in situ EXAFS to probe the H-2 assisted octane-SCR reaction has shown that small Ag particles (containing on average 3 silver atoms) are formed during the SCR reaction but that the addition of H-2 to the feed does not result in any further change in the Ag particle size. This points to the direct involvement of H-2 in the reaction mechanism. Clearly the addition of hydrogen results in a large increase in the number and variety of adsorbed species on the surface of the catalyst during the reaction. Some authors have suggested that conversion of cyanide to isocyanate is the rate-determining step and that hydrogen promotes this conversion. Others have suggested that hydrogen reduces nitrates to more reactive nitrite species which can then activate the hydrocarbon; activation of the hydrocarbon to form acetates has been proposed as the key step. It is probable that all these promotional effects can take place and that it very much depends on the reaction temperature and feed conditions as to which one is most important.

A review of the selective reduction of NOx, with hydrocarbons under lean-burn conditions with non-zeolitic oxide and platinum group metal catalysts

Research on the selective reduction of NOx with hydrocarbons under lean-burn conditions using non-zeolitic oxides and platinum group metal (PGM) catalysts has been critically reviewed. Alumina and silver-promoted alumina catalysts have been described in detail with particular emphasis on an analysis of the various reaction mechanisms that have been put forward in the literature. The influence of the nature of the reducing agent, and the preparation and structure of the catalysts have also been discussed and rationalised for several other oxide systems. It is concluded for non-zeolitic oxides that species that are strongly adsorbed on the surface, such as nitrates/nitrites and acetates, could be key intermediates in the formation of various reduced and oxidised species of nitrogen, the further reaction of which leads eventually to the formation of molecular nitrogen. For the platinum group metal catalysts, the different mechanisms that have been proposed in the literature have been critically assessed. It is concluded that although there is indirect, mainly spectroscopic, evidence for various reaction intermediates on the catalyst surface, it is difficult to confirm that any of these are involved in a critical mechanistic step because of a lack of a direct quantitative correlation between infrared and kinetic measurements. A simple mechanism which involves the dissociation of NO on a reduced metal surface to give N(ads) and O(ads), with subsequent desorption of N-2 and N2O and removal of O(ads) by the reductant can explain many of the results with the platinum group metal catalysts, although an additional contribution from organo-nitro-type species may contribute to the overall NOx reduction activity with these catalysts.

Sulfur-tolerant NOx storage traps: an infrared and thermodynamic study of the reactions of alkali and alkaline-earth metal sulfates

The sulfur tolerance of a barium-containing NOx storage/reduction trap was investigated using infrared analysis. It was confirmed that barium carbonate could be replaced by barium sulfate by reaction with low concentrations of sulfur dioxide (50 ppm) in the presence of large concentrations of carbon dioxide (10%) at temperatures up to 700 degreesC. These sulfates could at least be partially removed by switching to hydrogen-rich conditions at elevated temperatures. Thermodynamic calculations were used to evaluate the effects of gas composition and temperature on the various reactions of barium sulfate and carbonate under oxidizing and reducing conditions. These calculations clearly showed that if, under a hydrogen-rich atmosphere, carbon dioxide is included as a reactant and barium carbonate as a product then barium sulfate can be removed by reaction with carbon dioxide at a much lower temperature than is possible by decomposition to barium oxide. It was also found that if hydrogen sulfide was included as a product of decomposition of barium sulfate instead of sulfur dioxide then the temperature of reaction could be significantly lowered. Similar calculations were conducted using a selection of other alkaline-earth and alkali metals. In this case calculations were simulated in a gas mixture containing carbon monoxide, hydrogen and carbon dioxide with partial pressures similar to those encountered in real exhausts during switches to rich conditions. The results indicated that there are metals such as lithium and strontium with less stable sulfates than barium, which may also possess sufficient NOx storage capacity to give sulfur-tolerant NOx traps.

The application of NMR to study changes in polar metabolite concentrations in beef longissimus dorsi stored for different periods post mortem

In this study data generated by H-1 NMR spectroscopy were combined with chemometrics to analyse beef samples aged over a 21 day period. In particular, the amino acids, of which 12 were identified were found to increase over the ageing period with samples matured for 3 days having notably lower concentrations than carcasses aged for 21 days. This is believed to be a result of increased proteolysis within the muscle. This novel approach of using high resolution NMR spectrometry to analyse beef samples has not previously been reported and these findings demonstrate the potential of this technique linked with HPLC to be used as a suitable method for profiling meat samples.

Power Stored and Quality Factors in Frequency Selective Surfaces at THz Frequencies

A study of the external, loaded and unloaded quality factors for frequency selective surfaces (FSSs) is presented. The study is focused on THz frequencies between 5 and 30 THz, where ohmic losses arising from the conductors become important. The influence of material properties, such as metal thickness, conductivity dispersion and surface roughness, is investigated. An equivalent circuit that models the FSS in the presence of ohmic losses is introduced and validated by means of full-wave results. Using both full-wave methods as well as a circuit model, the reactive energy stored in the vicinity of the FSS at resonance upon plane-wave incidence is presented. By studying a doubly periodic array of aluminium strips, it is revealed that the reactive power stored at resonance increases rapidly with increasing periodicity. Moreover, it is demonstrated that arrays with larger periodicity-and therefore less metallisation per unit area-exhibit stronger thermal absorption. Despite this absorption, arrays with higher periodicities produce higher unloaded quality factors. Finally, experimental results of a fabricated prototype operating at 14 THz are presented.

The use of short time-on-stream in situ spectroscopic transient kinetic isotope techniques to investigate the mechanism of hydrocarbon selective catalytic reduction (HC-SCR) of NOx at low temperatures

The problem of differentiating between active and spectator species that have similar infrared spectra has been addressed by developing short time-on-stream in situ spectroscopic transient isotope experimental techniques (STOS-SSITKA). The techniques have been used to investigate the reaction mechanism for the reduction of nitrogen oxides (NOx) by hydrocarbons under lean-burn (excess oxygen) conditions on a silver catalyst. Although a nitrate-type species tracks the formation of isotopically labeled dinitrogen, the results show that this is misleading because a nitrate-type species has the same response to an isotopic switch even under conditions where no dinitrogen is produced. In the case of cyanide and isocyanate species, the results show that it is possible to differentiate between slowly reacting spectator isocyanate species, probably adsorbed on the oxide support, and reactive isocyanate species, possibly on or close to the active silver phase. The reactive isocyanate species responds to an isotope switch at a rate that matches that of the rate of formation of the main product, dinitrogen. It is concluded that these reactive isocyanates could potentially be involved in the reduction of NOx whereas there is no evidence to support the involvement of nitrate-type species that are observable by infrared spectroscopy.

Investigating the mechanism of the H 2-assisted selective catalytic reduction (SCR) of NOx with octane using fast cycling transient in situ DRIFTS-MS analysis

A mechanistic study of the H-2-assisted Selective Catalytic Reduction (SCR) of NOx with octane as reductant over a Ag/Al2O3 catalyst was carried out using a modified DRIFTS cell coupled to a mass spectrometer Using fast transient cycling switching of H-2 with a time resolution of a few seconds It was possible to differentiate potential reaction intermediates from other moieties that are clearly spectator species Using such a periodic operation mode effects were uncovered that are normally hidden in conventional transient studies which typically consist of a single transient In experiments based on a single transient addition of H-2 to or removal of H-2 from the SCR feed it was found that the changes in the concentrations of gaseous species (products and reactants) were not matched by changes at comparable timescales of the concentration of surface species observed by IR This observation indicates that the majority of sur face species observed by DRIFTS under steady-state reaction conditions are spectators In contrast under fast cycling experimental conditions It was found that a surface isocyanate species had a temporal response that matched that of N-15(2) This suggests that some of the isocyanate species observed by infrared spectroscopy could be important intermediates in the hydrogen-assisted SCR reaction although it is emphasised that this may be dependent on the way in which the infrared spectra are obtained It is concluded that the use of fast transient cycling switching techniques may provide useful mechanistic information under certain circumstances.