Nitrogen oxide adsorption

An additional benefit of adsorption-based sulfur dioxide removal processes is that nitrogen oxides, NO, are also removed by the sorbent. Nitrogen oxides desorb when the sorbent is heated using hot air. 

In contrast, for the NO8- species the N—O bond is elongated, only slightly polarized, and the stretching frequency, vNO, decreases below 1850 cm-1. Such changes indicate that the activation consists in redistribution of the electron and spin densities within the M—NO unit, which accumulates on the nitrogen atom. Among the first series TMI, the oxidative adsorption is less common and includes only the tj1 CuNO] 11 and 171 3CrNO 6 adducts. The mechanistic implications of the electronic structures for both type of the nitrosyl complexes are discussed in the next section. 

Abstract A review is provided on the contribution of modern surface-science studies to the understanding of the kinetics of DeNOx catalytic processes. A brief overview of the knowledge available on the adsorption of the nitrogen oxide reactants, with specific emphasis on NO, is provided first. A presentation of the measurements of NO, reduction kinetics carried out on well-characterized model system and on their implications on practical catalytic processes follows. Focus is placed on isothermal measurements using either molecular beams or atmospheric pressure environments. That discussion is then complemented with a review of the published research on the identification of the key reaction intermediates and on the determination of the nature of the active sites under realistic conditions. The link between surface-science studies and molecular computational modeling such as DFT calculations, and, more generally, the relevance of the studies performed under ultra-high vacuum to more realistic conditions, is also discussed. 

Numerous quantum mechanic calculations have been carried out to better understand the bonding of nitrogen oxide on transition metal surfaces. For instance, the group of Sautet et al have reported a comparative density-functional theory (DFT) study of the chemisorption and dissociation of NO molecules on the close-packed (111), the more open (100), and the stepped (511) surfaces of palladium and rhodium to estimate both energetics and kinetics of the reaction pathways [75], The structure sensitivity of the adsorption was found to correlate well with catalytic activity, as estimated from the calculated dissociation rate constants at 300 K. The latter were found to agree with numerous experimental observations, with (111) facets rather inactive towards NO dissociation and stepped surfaces far more active, and to follow the sequence Rh(100) > terraces in Rh(511) > steps in Rh(511) > steps in Pd(511) > Rh(lll) > Pd(100) > terraces in Pd (511) > Pd (111). The effect of the steps on activity was found to be clearly favorable on the Pd(511) surface but unfavorable on the Rh(511) surface, perhaps explaining the difference in activity between the two metals. The influence of... 

Air/liquid (A/L) interface, adsorption of surfactants at, 24 133-138 Air mass zero (AMO) spectrum, 23 37 Air monitoring, for hydrazine, 13 589 Air oxidized pan, 11 194 Air-path XRF, in fine art examination/ conservation, 11 403—404 Air pollutants. See also Nitrogen oxides (NO j Particulate matter Sulfur oxides (SOJ Volatile organic compounds (VOCs) air toxics, 1 789, 801-802 carbon monoxide, 1 789, 798 common, 26 667 criteria pollutants, l 813t indoor, 1 802-805, 820-823, 821t lead, 1 789, 801... 

Adsorption of nitric and sulfuric acids on ice particles provides the sol of the nitrating mixture. An important catalyst of aromatic nitration, nitrous acid, is typical for polluted atmospheres. Combustion sources contribute to air pollution via soot and NO emissions. The observed formation of HNO2 results from the reduction of nitrogen oxides in the presence of water by C—O and C—H groups in soot (Ammann et al. 1998). As seen, gas-phase nitration is important ecologically. 

The coordinative and/or dissociative adsorption of various probe molecules has been used to characterize the surface properties of Ti02) which finds applications as a catalyst, photocatalyst, and sensor. Among the molecules used as probes, we mention CO (37, 38, 563-576), C02 (563, 565, 577), NO (578,579), water (580,581), pyridine (582,583), ammonia (584,585), alcohols (586, 587), ethers (including perfluoroethers) (588), ozone (589), nitrogen oxide (590), dioxygen (591), formic acid (592-594), benzene (584), benzoic acid (595), and chromyl chloride (596). 

The inherent ability of selective catalytic reduction (SCR) catalysts for stack gas denitrification to store ammonia adsorptively can be exploited with appropriate control algorithms to damp out the influence of fluctuations in the amount of gas and level of nitrogen oxides being treated. Moreover, it also forms the basis of the adsorptive reactor concept for the total denitrification of flue gases without ammonia... 

Some workers examined Pt-cata)yst deactivation by nitrate poisoning11 15 and they estimated that the deactivation might result from the adsorption of the nitrogen oxides that were produced from nitrate by decomposition. To check their results, we introduced NO or N02 gas directly into the reactor and measured the reaction rate The gas composed of l. 2% NO, or 1.7% N02, 28% H20 and the balance of H2. However, no deactivation was observed, and on the contrary the reaction rate was accelerated probably by the exothermic reactions between nitrogen oxides and hydrogen. 

Zeolites have also proven applicable for removal of nitrogen oxides (NO ) from wet nitric acid plant tail gas (59) by the UOP PURASIV N process (54). The removal of NO from flue gases can also be accomplished by adsorption. The Unitaka process utilizes activated carbon with a catalyst for reaction of NO, with ammonia, and activated carbon has been used to convert NO to N02, which is removed by scrubbing (58). Mercury is another pollutant that can be removed and recovered by TSA. Activated carbon impregnated with elemental sulfur is effective for removing Hg vapor from air and other gas streams the Hg can be recovered by ex situ thermal oxidation in a retort (60). The UOP PURASIV Hg process recovers Hg from clilor-alkali plant vent streams using more conventional TSA regeneration (54). Mordenite and clinoptilolite zeolites are used to remove HQ from Q2, clilorinated hydrocarbons, and reformer catalyst gas streams (61). Activated aluminas are also used for such applications, and for the adsorption of fluorine and boron—fluorine compounds from alkylation (qv) processes (50). 

Recently, rotor-type adsorption systems attract much attention, because the systems can effectively control humidity and air pollutants such as volatile organic compounds (VOCs), nitrogen oxide (NOx) and sulfiuic oxide (SOx). Gas remediation efficiency is principally concerned to the gas capturing ability of the adsorbents impregnated into the ceramic honeycomb rotor such as zeolite, silica, activated carbon, etc. Therefore, it is one of the most important works to develop the adsorbent with good absorption-desorption behaviors. 

THERMAL AND SURFACE MECHANISM STUDIES ON ADSORPTION-TEMPERATURE PROGRAMMED DESORPTION OF NITROGEN OXIDES OVER CHEMICALLY ACTIVATED CARBON FIBER... 

---