Role of active oxygen transients in selective catalytic reduction of N2O with CH4 over Fe-zeolite catalysts

Sharp NO and O₂ desorption peaks, which were caused by the decomposition of nitro and nitrate species over Fe species, were observed in the range of 520–673 K in temperature-programmed desorption (TPD) from Fe-MFI after H₂ treatment at 773 K or high-temperature (HT) treatment at 1073 K followed by N₂O treatment. The amounts of O₂ and NO desorption were dependent on the pretreatment pressure of N₂O in the H₂ and N₂O treatment. The adsorbed species could be regenerated by the H₂ and N₂O treatment after TPD, and might be considered to be active oxygen species in selective catalytic reduction (SCR) of N₂O with CH₄. However, the reaction rate of CH₄ activation by the adsorbed species formed after the H₂ and N₂O or the HT and N₂O treatment was not so high as that of the CH₄ + N₂O reaction over the catalyst after O₂ treatment. The simultaneous presence of CH₄ and N₂O is essential for the high activity of the reaction, which suggests that nascent oxygen species formed by N₂O dissociation can activate CH₄ in the SCR of N₂O with CH₄.     

Catalytic reduction of N2O over steam-activated FeZSM-5 zeolite: Comparison of CH4, CO, and their mixtures as reductants with or without excess O2

The catalytic reduction of N₂O by CH₄, CO, and their mixtures has been comparatively investigated over steam-activated FeZSM-5 zeolite. The influence of the molar feed ratio between N₂O and the reducing agents, the gas-hourly space velocity, and the presence of O₂ on the catalytic performance were studied in the temperature range of 475–850 K. The CH₄ is more efficient than CO for N₂O reduction, achieving the same degree of conversion at significantly lower temperatures. The apparent activation energy for N₂O reduction by CH₄ was very similar to that of direct N₂O decomposition (140 kJ mol⁻¹), being much lower for the N₂O reduction by CO (60 kJ mol⁻¹). This suggests that the reactions have a markedly different mechanism. Addition of CO using equimolar mixtures in the ternary N₂O + CH₄ + CO system did not affect the N₂O conversion with respect to the binary N₂O + CH₄ system, indicating that CO does not interfere in the low-temperature reduction of N₂O by CH₄. In the ternary system, CO contributed to N₂O reduction when methane was the limiting reactant. The conversion and selectivity of the reactions of N₂O with CH₄, CO, and their mixtures were not altered upon adding excess O₂ in the feed.     

Surface-nitrogen removal in NO and N2O reduction on Pd(1 1 0): Angular distribution studies of desorbing products

This paper is a report of angle-resolved product desorption measurements in the course of catalyzed NO and N₂O reduction on Pd(1 1 0). Surface-nitrogen removal processes show different angular distributions, i.e. normally directed N₂ desorption takes place in process (i) 2N(a) → N₂(g). Highly inclined N₂ desorption towards the [0 0 1] direction is induced in process (ii) N₂O(a) → N₂(g) + O(a). N₂O or NH₃ desorption follows the cosine distribution characterizing the desorption after the thermalization in process (iii) N₂O(a) → N₂O(g) or (iv) N(a) + 3H(a) → NH₃(a) → NH₃(g). Thus, a combination of the angular and velocity distributions provides the analysis of most of surface-nitrogen removal processes in the course of catalyzed NO reduction.

At temperatures below 600 K, processes (ii) and (iii) dominate and process (iv) is enhanced at H₂ pressures higher than NO. Process (i) contributes significantly above 600 K. Only three processes except for NH₃ formation are operative when CO is used. Only process (ii) was observed in a steady-state N₂O + CO (or H₂) reaction.     

Development of a new Rh/TiO2–sepiolite monolithic catalyst for N2O decomposition

Monolithic catalysts based on Rh/TiO₂–sepiolite were developed and tested in the decomposition of N₂O traces. Several effects such as the presence of NO, O₂ and NO + O₂ in the gas mixture, the catalysts pre-treatment and the metal loading were evaluated. The system was extremely sensitive to the amount of rhodium, passing through a maximum in the catalytic activity at a Rh content of 0.2 wt.%. It has been demonstrated that both NO and O₂ compete for the same adsorption sites as N₂O; however, this effect was not as severe as for other previously reported Rh systems. For NO + O₂ gas mixtures the inhibition effect was stronger than when only NO or O₂ was present. Analysis of the pre-reduced sample by XPS showed Rh mainly in the metal state, even after treatment with N₂O + O₂ mixtures, suggesting that the oxygen consumption observed in the Temperature Programmed Reaction experiments was related to the oxygen uptake by vacancies in the support. The presence of sepiolite in the support preparation and its role as a matrix over which TiO₂ particles were distributed, seems to play an important effect in the migration process of oxygen species through the support vacancies. The Rh/TiO₂ monolithic system is an attractive alternative for the elimination of N₂O traces from stationary sources due to the combination of high catalytic activity with a low pressure drop and optimum textural/mechanical properties.     

Water vapor sensitivity of nanosized La(Co, Mn, Fe)1−x(Cu, Pd)xO3 perovskites during NO reduction by C3H6 in the presence of oxygen

A series of La(Co, Mn, Fe)_1−x(Cu, Pd)_xO₃ perovskites having high specific surface areas and nanosized crystal domains was prepared by reactive grinding. The solids were characterized by N₂ adsorption, X-ray diffraction (XRD), scanning electron microscopy (SEM), temperature programmed desorption (TPD) of O₂, NO + O₂, C₃H₆, in the absence or presence of 5% H₂O, Fourier transform infrared (FTIR) spectroscopy, as well as activity tests towards NO reduction by propene under the conditions of 3000 ppm NO, 3000 ppm C₃H₆, 1% O₂, 0 or 10% H₂O, and 50,000 h⁻¹ space velocity. The objective was to investigate the influence of H₂O addition on catalytic behavior. A good performance (100% NO conversion, 77% N₂ yield, and 90% C₃H₆ conversion) was achieved at 600 °C over LaFe_0.8Cu_0.2O₃ under a dry feed stream. With the exposure of LaFe_0.8Cu_0.2O₃ to a humid atmosphere containing 10% water vapor, the catalytic activity was slightly decreased yielding 91% NO conversion, 51% N₂ yield, and 86% C₃H₆ conversion. A competitive adsorption between H₂O vapor with O₂ and NO molecules at anion vacancies over LaFe_0.8Cu_0.2O₃ was found by means of TPD studies here. A deactivation mechanism was therefore proposed involving the occupation of available active sites by water vapor, resulting in an inhibition of catalytic activity in C₃H₆ + NO + O₂ reaction. This H₂O deactivation was also verified to be strictly reversible by removing steam from the feed.     

The origin of N2O formation in the selective catalytic reduction of NOx by NH3 in O2 rich atmosphere on Cu-faujasite catalysts

The selective catalytic reduction (SCR) of NO_x (NO + NO₂) by NH₃ in O₂ rich atmosphere has been studied on Cu-FAU catalysts with Cu nominal exchange degree from 25 to 195%. NO₂ promotes the NO conversion at NO/NO₂ = 1 and low Cu content. This is in agreement with next-nearest-neighbor (NNN) Cu ions as the most active sites and with N_xO_y adsorbed species formed between NO and NO₂ as a key intermediate. Special attention was paid to the origin of N₂O formation. CuO aggregates form 40–50% of N₂O at ca. 550 K and become inactive for the SCR above 650 K. NNN Cu ions located within the sodalite cages are active for N₂O formation above 600 K. This formation is greatly enhanced when NO₂ is present in the feed, and originated from the interaction between NO (or NO₂) and NH₃. The introduction of selected co-cations, e.g. Ba, reduces very significantly this N₂O formation.     

Effect of different oxygen species originating from the dissociation of O2, N2O and NO on the selectivity of the Pt-catalysed NH3 oxidation

An effect of oxygen species formed from O₂, N₂O and NO on the selectivity of the catalytic oxidation of ammonia was studied over a polycrystalline Pt catalyst using the temporal analysis of products (TAP) reactor. The transient experiments were performed in the temperature range between 773 and 1073 K in a sequential pulse mode with a time interval of 0.2 s between the pulses of the oxidant (O₂, N₂O and NO) and NH₃. In contrast to adsorbed oxygen species formed from NO, those from O₂ and N₂O reacted with ammonia yielding NO. It is suggested that the difference between these oxidising agents may be related to the different active sites for dissociation of O₂, N₂O and NO, where oxygen species of various Pt-O strength are formed. Weaker bound oxygen species, which are active for NO formation, originate from O₂ and N₂O rather than from NO. These species may be of bi-atomic nature.     

A combination of NOx trapping materials and urea-SCR catalysts for use in the removal of NOx from mobile diesel engines

Preliminary studies on a series of nanocomposite BaO–Fe ZSM-5 materials have been carried out to determine the feasibility of combining NO_x trapping and SCR-NH₃ reactions to develop a system that might be applicable to reducing NO_x emissions from diesel-powered vehicles. The materials are analysed for SCR-NH₃ and SCR-urea reactivity, their NO_x trapping and NH₃ trapping capacities are probed using temperature programmed desorption (TPD) and the activities of the catalysts for promoting the NH_{3 ads} + NO/O₂ → N₂ and NO_{x ads} + NH₃ → N₂ reactions are studied using temperature programmed surface reaction (TPSR).     

High combustion activity of methane induced by reforming gas over Ni/Al2O3 catalysts

During the reactions related to oxidative steam reforming and combustion of methane over -alumina-supported Ni catalysts, the temperature profiles of the catalyst bed were studied using an infrared (IR) thermograph. IR thermographical images revealed an interesting result: that the temperature at the catalyst bed inlet is much higher under CH₄/H₂O/O₂/Ar = 20/10/20/50 than under CH₄/H₂O/O₂/Ar = 10/0/20/70; the former temperature is comparable to that over noble metal catalysts such as Pt and Pd. Based on the temperature-programmed reduction and oxidation measurements over fresh and used catalysts, the metallic Ni is recognized at the catalyst bed inlet under CH₄/H₂O/O₂/Ar = 20/10/20/50, although it is mainly oxidized to NiAl₂O₄ under CH₄/H₂O/O₂/Ar = 10/0/20/70. This result indicates that the addition of reforming gas (CH₄/H₂O = 10/10) to the combustion gas (CH₄/O₂ = 10/20) can stabilize Ni species in the metallic state even under the presence of oxygen in the gas phase. This would account for its extremely high combustion activity.     

Temperature programmed desorption study of adsorbed species formed by the decomposition of N2O on ion-exchanged copper zeolite catalysts

The nature of the adsorbed species on Cu-ZSM-5 (Cu-Z), Cu-Mordenite (Cu-M), and Cu-Y-zeolite (Cu-Y) was investigated by means of temperature programmed desorption (TPD). When dinitrogen monoxide (N₂O) came into contact with Cu-zeolites above 573 K, the decomposition of N₂O occurred accompanied by the formation of adsorbed oxygen species and adsorbed nitrogen oxide species. In the TPD runs, three O₂ desorption peaks appeared at temperatures of 623, 673, and 753 K and were named -, β-, and γ-peaks, respectively. The O₂ desorption at the - and γ-peaks became quickly saturated after contacting N₂O at 598 K, while the amount of O₂ desorbed at the β-peak increased with time, not reaching a constant level until 120 min of exposure. The activity for the decomposition of N₂O decreased with the accumulation of β-oxygen over the catalyst. The rate of N₂O decomposition depended upon the nature and amount of the copper zeolite catalysts available, as determined by the formation of - and/or β-oxygen.     

NO decomposition and reduction by CH4 over Sr/La2O3

Both NO decomposition and NO reduction by CH₄ over 4%Sr/La₂O₃ in the absence and presence of O₂ were examined between 773 and 973 K, and N₂O decomposition was also studied. The presence of CH₄ greatly increased the conversion of NO to N₂ and this activity was further enhanced by co-fed O₂. For example, at 773 K and 15 Torr NO the specific activities of NO decomposition, reduction by CH₄ in the absence of O₂, and reduction with 1% O₂ in the feed were 8.3·10⁻⁴, 4.6·10⁻³, and 1.3·10⁻² μmol N₂/s m², respectively. This oxygen-enhanced activity for NO reduction is attributed to the formation of methyl (and/or methylene) species on the oxide surface. NO decomposition on this catalyst occurred with an activation energy of 28 kcal/mol and the reaction order at 923 K with respect to NO was 1.1. The rate of N₂ formation by decomposition was inhibited by O₂ in the feed even though the reaction order in NO remained the same. The rate of NO reduction by CH₄ continuously increased with temperature to 973 K with no bend-over in either the absence or the presence of O₂ with equal activation energies of 26 kcal/mol. The addition of O₂ increased the reaction order in CH₄ at 923 K from 0.19 to 0.87, while it decreased the reaction order in NO from 0.73 to 0.55. The reaction order in O₂ was 0.26 up to 0.5% O₂ during which time the CH₄ concentration was not decreased significantly. N₂O decomposition occurs rapidly on this catalyst with a specific activity of 1.6·10⁻⁴ μmol N₂/s m² at 623 K and 1220 ppm N₂O and an activation energy of 24 kcal/mol. The addition of CH₄ inhibits this decomposition reaction. Finally, the use of either CO or H₂ as the reductant (no O₂) produced specific activities at 773 K that were almost 5 times greater than that with CH₄ and gave activation energies of 21–26 kcal/mol, thus demonstrating the potential of using CO/H₂ to reduce NO to N₂ over these REO catalysts.     

The bifunctional reaction pathway and dual kinetic regimes in NOx SCR by methane over cobalt mordenite catalysts

The pathway for selective reduction of NO_x by methane over Co mordenite cataysts has been studied by comparing the rates of the individual reactions (NO oxidation, CH₄ oxidation, NO₂ reduction) with that of the combined reaction (NO + O₂ + CH₄). Co⁽⁺²⁾ was exchanged into H-MOR and Na-MOR to give catalysts with different metal loading and number of support protons. Additionally, exchanged Co⁽⁺²⁾ ions were precipitated with NaOH to produce dispersed cobalt oxide on Na-MOR. The NO oxidation rate is the same for ion exchanged Co⁽⁺²⁾ ions in H-MOR and Na-MOR, but the rate of Co⁽⁺²⁾ ions is much lower than that of cobalt oxide. NO oxidation equilibrium is obtained only for those catalysts with high metal loading, cobalt oxide or run at low GHSV. Under the conditions of selective catalytic reduction, methane oxidation by O₂ is low for all catalysts. The turnover frequency of Co on Na-MOR, however, is higher than that on H-MOR. The rate of NO₂ reduction to N₂ is directly proportional to the number of support acid sites and independent of the amount of Co. Comparison of the rates and selectivities for the individual reactions with the combined reaction of NO + O₂ + CH₄ indicates that there are two types of catalysts. For the first, the NO oxidation is in equilibrium and the rate determining step is reduction of NO₂. For these catalysts, the rate (and selectivity) for formation of N₂ is identical from NO + O₂ + CH₄ and NO₂ + CH₄. These catalysts have high metal loading and few acid sites. Nevertheless, the rate of N₂ formation increases with increasing number of protons. For the second type of catalyst, NO oxidation is not in equilibrium and is the rate limiting step. For these catalysts the rate of N₂ formation increases with increasing metal loading. Neither catalyst type, however, is optimized for the maximum formation of N₂. By using a mixture of catalysts, one with high NO oxidation activity and one with a large number of Brønsted acid sites, the rate of N₂ is greater than the weighted sum of the individual catalysts. The current results support the proposal that the pathway for selective catalytic reduction is bifunctional where metal sites affect NO oxidation, while support protons catalyze the formation of N₂.     

Nitrous oxide reduction with ammonia over Co---MgO catalyst and the influence of excess oxygen

N₂O decomposition on Co---MgO was studied under high (6.67 kPa) and low (75 Pa) N₂O pressure and the effect of reductant (C₂H₆, NH₃) was studied. The activity decays because of the strong adsorption of oxygen produced, while the reductant removed the adsorbed oxygen giving a steady catalysis. The reaction between NH₃ and excess amount of O₂ produced N₂O as a main product. Although N₂O gives the same intermediate (O) as O₂ does, the former decomposition seems to proceed faster than the latter on Co---MgO. The reaction mechanism studied here was compared with the SCR (NO---NH₃ in O₂) reaction on V₂O₂-TiO₂. Since NH₃, N₂O and O₂ gives only N₂ and water, Co---MgO can be a possible catalyst used in the boiler exhaust to reduce N₂O concentration by adding ammonia.     

Inhibition effect of H2O on V2O5/AC catalyst for catalytic reduction of NO with NH3 at low temperature

The inhibition effect of H₂O on V₂O₅/AC catalyst for NO reduction with NH₃ is studied at temperatures up to 250 °C through TPD, elemental analyses, temperature-programmed surface reaction (TPSR) and FT-IR analyses. The results show that H₂O does not reduce NO and NH₃ adsorption on V₂O₅/AC catalyst surface, but promotes NH₃ adsorption due to increases in Brønsted acid sites. Many kinds of NH₃ forms present on the catalyst surface, but only NH₄⁺ on Brønsted acid sites and a small portion of NH₃ on Lewis acid sites are reactive with NO at 250 °C or below, and most of the NH₃ on Lewis acid sites does not react with NO, regardless the presence of H₂O in the feed gas. H₂O inhibits the SCR reaction between the NH₃ on the Lewis acid sites and NO, and the inhibition effect increases with increasing H₂O content. The inhibition effect is reversible and H₂O does not poison the V₂O₅/AC catalyst.     

Micro-kinetic analysis of direct N2O decomposition over steam-activated Fe-silicalite from transient experiments in the TAP reactor

Mechanistic and kinetic aspects of the direct decomposition of N₂O over steam-activated Fe-silicalite were investigated by transient experiments in vacuum (N₂O peak pressure of ca. 10 Pa) using the temporal analysis of products (TAP) reactor in the temperature range of 773–848 K. The transient responses of N₂O, N₂, and O₂ obtained upon N₂O decomposition were fitted to different micro-kinetic models. Through model discrimination it was concluded that both free iron sites and iron sites with adsorbed mono-atomic oxygen (*O) species are active for N₂O decomposition. Oxygen formation occurs via decomposition of bi-atomic (*O₂) oxygen species adsorbed over the iron site. This bi-atomic oxygen species originates from another bi-atomic oxygen species (O*O), which is initially formed via interaction of N₂O with iron site possessing mono-atomic oxygen species (*O). Based on our modeling, the recombination of two mono-atomic oxygen (*O) species or direct O₂ formation via reaction of N₂O with *O can be excluded as potential reaction pathways yielding gas-phase O₂. The simulation results predict that the overall rate of N₂O decomposition is controlled by regeneration of free iron sites via a multi-step oxygen formation at least below 700 K.     

Mechanistic peculiarities of the N2O reduction by CH4 over Fe-silicalite

Transient isotopic studies in the temporal analysis of products (TAP) reactor evidenced the importance of the lifetime of oxygen species generated upon N₂O decomposition on extraframework iron sites of Fe-silicalite for methane oxidation at 723 K. Fe-silicalite effectively activates CH₄ when N₂O and CH₄ are pulsed together in the reactor. However, these oxygen species gradually become inactive for methane oxidation as the time delay between the N₂O and CH₄ pulses is increased from 0 to 2 s.     

Catalytic reduction of NOx with H2/CO/CH4 over PdMOR catalysts

Conversion of NO_x with reducing agents H₂, CO and CH₄, with and without O₂, H₂O, and CO₂ were studied with catalysts based on MOR zeolite loaded with palladium and cerium. The catalysts reached high NO_x to N₂ conversion with H₂ and CO (>90% conversion and N₂ selectivity) range under lean conditions. The formation of N₂O is absent in the presence of both H₂ and CO together with oxygen in the feed, which will be the case in lean engine exhaust. PdMOR shows synergic co-operation between H₂ and CO at 450–500 K. The positive effect of cerium is significant in the case of H₂ and CH₄ reducing agent but is less obvious with H₂/CO mixture and under lean conditions. Cerium lowers the reducibility of Pd species in the zeolite micropores. The catalysts showed excellent stability at temperatures up to 673 K in a feed with 2500 ppm CH₄, 500 ppm NO, 5% O₂, 10% H₂O (0–1% H₂), N₂ balance but deactivation is noticed at higher temperatures. Combining results of the present study with those of previous studies it shows that the PdMOR-based catalysts are good catalysts for NO_x reduction with H₂, CO, hydrocarbons, alcohols and aldehydes under lean conditions at temperatures up to 673 K.     

NO removal by CH4 on Co-NaX-CO and Ag-NaX catalysts in a dual-bed system

NO removal using CH₄ as a reductant in a dual-bed system has been investigated with Co-NaX and Ag-NaX catalysts, which were prepared by Co²⁺-, Ag⁺-ion exchange into zeolite NaX, respectively, and activation for 5 h at 500 °C. The experimental result has been compared with that of a Co-NaX-CO catalyst, additionally pre-treated under CO flow for the Co-NaX catalyst. The cobalt crystal structure of a Co-NaX-CO catalyst is Co₃O₄, which promotes NO oxidation to NO₂ by excess O₂ at a low temperature (523 K). The mechanical mixture of Co-NaX-CO and Ag-NaX catalysts shows a synergy effect on NO reduction to N₂ by CH₄ in the presence of excess O₂ and H₂O, but the NO reduction decreases quickly as time passes. However, the NO reduction to N₂ in a deNO bed at 523 K and a deNO₂ bed at 423 K, which are relatively lower than the reaction temperatures for common SCR systems, still remained at 67% even in a H₂O 10% gas mixture after 160 min.     

High thermal conductive β-SiC for selective oxidation of H2S: A new support for exothermal reactions

This study aims at synthesizing a new by substituting 1 atom% Pd²⁺ in ionic state in TiO₂ in the form of Ti_0.99Pd_0.01O_1.99 with oxide-ion vacancy. The catalyst was synthesized by solution combustion method and was characterized by XRD and XPS. The catalytic activity was investigated by performing CO oxidation, hydrocarbon oxidation and NO reduction. A reaction mechanism for CO oxidation by O₂ and NO reduction by CO was proposed. The model based on CO adsorption on Pd²⁺ and dissociative chemisorption of O₂ in the oxide-ion vacancy for CO oxidation reaction fitted the experimental for CO oxidation. For NO reduction in presence of CO, the model based on competitive adsorption of NO and CO on Pd²⁺, NO chemisorption and dissociation on oxide-ion vacancy fitted the experimental data. The rate parameters obtained from the model indicated that the reactions were much faster over this catalyst compared to other catalysts reported in the literature. The selectivity of N₂, defined as the ratio of the formation of N₂ and formation of N₂ and N₂O, was very high compared to other catalysts and 100% selectivity was reached at temperature of 350 °C and above. As the N₂O + CO reaction is an intermediate reaction for NO + CO reaction, it was also studied as an isolated reaction and the rate of the isolated reaction was less than that of intermediate reaction.