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.     

Characterization and performance of Pt-USY in the SCR of NOx with hydrocarbons under lean-burn conditions

Pt-USY was used for the selective catalytic reduction of NO_x with hydrocarbons in the presence of excess oxygen. The catalyst was prepared by an ion-exchange method and characterized by XRD, TEM, CO chemisorption, and Ar adsorption at 87 K. The platinum particle size distribution was found to be broad (2–20 nm), with no apparent sintering of the active phase during the HC-SCR process after 25 h time-on-stream. Generally, large metal clusters (>15 nm) are situated at the external surface of the zeolite, while the smaller ones are located in the pores of the support. Pt-USY shows an excellent activity in the deNO_x reaction (molar NO_x conversion 90% at 475 K) with propene as the reductant in 5 kPa O₂, as well as stable operation during time-on-stream. Propane only yields a low NO_x conversion compared to propene. The presence of high oxygen contents (5–10 kPa O₂) slightly inhibits the reaction. No significant decrease in deNO_x activity was observed at high space velocities (up to 100,000 h⁻¹). The presence of SO₂ and H₂O in the feed stream did not significantly affect the deNO_x activity. Pt-USY performs better under lean-burn conditions than other Pt-catalysts supported on e.g. ZSM-5, Al₂O₃, or SiO₂. The selectivity to N₂ was similar to the other Pt-based catalysts (30%), the other major product being N₂O.     

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.     

Quantified NOx adsorption on Pt/K/gamma-Al2O3 and the effects of CO2 and H2O

A multi-component NO_x-trap catalyst consisting of Pt and K supported on γ-Al₂O₃ was studied at 250 °C to determine the roles of the individual catalyst components, to identify the adsorbing species during the lean capture cycle, and to assess the effects of H₂O and CO₂ on NO_x storage. The Al₂O₃ support was shown to have NO_x trapping capability with and without Pt present (at 250 °C Pt/Al₂O₃ adsorbs 2.3 μmols NO_x/m²). NO_x is primarily trapped on Al₂O₃ in the form of nitrates with monodentate, chelating and bridged forms apparent in Diffuse Reflectance mid-Infrared Fourier Transform Spectroscopy (DRIFTS) analysis. The addition of K to the catalyst increases the adsorption capacity to 6.2 μmols NO_x/m², and the primary storage form on K is a free nitrate ion. Quantitative DRIFTS analysis shows that 12% of the nitrates on a Pt/K/Al₂O₃ catalyst are coordinated on the Al₂O₃ support at saturation.

When 5% CO₂ was included in a feed stream with 300 ppm NO and 12% O₂, the amount of K-based nitrate storage decreased by 45% after 1 h on stream due to the competition of adsorbed free nitrates with carboxylates for adsorption sites. When 5% H₂O was included in a feed stream with 300 ppm NO and 12% O₂, the amount of K-based nitrate storage decreased by only 16% after 1 h, but the Al₂O₃-based nitrates decreased by 92%. Interestingly, with both 5% CO₂ and 5% H₂O in the feed, the total storage only decreased by 11%, as the hydroxyl groups generated on Al₂O₃ destabilized the K–CO₂ bond; specifically, H₂O mitigates the NO_x storage capacity losses associated with carboxylate competition.     

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.     

Influence of CO2 and H2O on NOx storage and reduction on a Pt–Ba/γ-Al2O3 catalyst

In this paper, the effect of CO₂ and H₂O on NO_x storage and reduction over a Pt–Ba/γ-Al₂O₃ (1 wt.% Pt and 30 wt.% Ba) catalyst is shown. The experimental results reveal that in the presence of CO₂ and H₂O, NO_x is stored on BaCO₃ sites only. Moreover, H₂O inhibits the NO oxidation capability of the catalyst and no NO₂ formation is observed. Only 16% of the total barium is utilized in NO storage. The rich phase shows 95% selectivity towards N₂ as well as complete regeneration of stored NO. In the presence of CO₂, NO is oxidized into NO₂ and more NO_x is stored as in the presence of H₂O, resulting in 30% barium utilization. Bulk barium sites are inactive in NO_x trapping in the presence of CO₂·NH₃ formation is seen in the rich phase and the selectivity towards N₂ is 83%. Ba(NO₃)₂ is always completely regenerated during the subsequent rich phase. In the absence of CO₂ and H₂O, both surface and bulk barium sites are active in NO_x storage. As lean/rich cycling proceeds, the selectivity towards N₂ in the rich phase decreases from 82% to 47% and the N balance for successive lean/rich cycles shows incomplete regeneration of the catalyst. This incomplete regeneration along with a 40% decrease in the Pt dispersion and BET surface area, explains the observed decrease in NO_x storage.     

The effect of hydrogen on the selective catalytic reduction of NO in excess oxygen over Ag/Al2O3

The selective catalytic reduction (SCR) of nitrogen oxides (NO_x) by propane in the presence of H₂ on sol–gel prepared Ag/Al₂O₃ catalysts (0.5–5 wt.% Ag) was investigated. It was confirmed that hydrocarbon-assisted SCR of NO_x is remarkably enhanced by co-feeding hydrogen to a lean exhaust gas mixture (λ>1), attaining considerable activity within a wide temperature window (470–825 K). The samples had marginal activity at 575 K without co-fed H₂, but achieved up to 60% NO_x conversion in the presence of H₂ at a space velocity of 30,000 h⁻¹. NO₂ as NO_x feed component is not converted to N₂ by C₃H₈ to a substantial extent under lean conditions. This points to an activation route of NO through direct conversion to adsorbed nitrite/nitrate or to a dissociation of NO over Ag⁰, formed through short-term reduction by H₂. The nature of Ag species was characterized by X-ray diffraction, temperature-programmed reduction, pulse thermoanalytical measurements, electron microscopy and FTIR spectroscopy. It could be shown that Ag₂O nano-sized clusters are predominantly present on all samples, whereas formation of silver aluminate could not be confirmed. Nano-sized Ag₂O clusters can reversibly be reduced/reoxidized by H₂. A silver loading higher than 2 wt.% leads to a part of Ag₂O particles, which are thermally decomposed during calcination at 800 K or higher. The catalytic role of this metallic silver is still unclear. Formal kinetic analysis of catalytic data revealed that the activation energy of the overall reaction is significantly lowered in the presence of H₂. The presence of water does not change the activation energy. It is concluded that hydrogen reduces the nano-sized Ag₂O clusters to Ag⁰ on a short-term scale. Zero-valent silver promotes a dissociation pathway of NO_x conversion. The fact that more oxidized ad-species (nitrite/nitrate) are observed in the presence of H₂ is attributed to a dissociative activation of gas-phase oxygen on Ag⁰.     

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 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.     

High temperature catalytic combustion of methane and propane over hexaaluminate catalysts: NOx emission characteristics

Several hexaaluminate-related materials were prepared via hydrolysis of alkoxide and powder mixing method for high temperature combustion of CH₄ and C₃H₈, in order to investigate the effect of the concentration of the fuels, O₂ and H₂O on NO_x emission and combustion characteristics. Among the hexaaluminate catalysts, Sr_0.8La_0.2MnAl₁₁O₁₉₋ prepared by the alkoxide method exhibited the highest activity for methane combustion and low NO_x emission capability. NO_x emission at 1500 °C was increased linearly with O₂ concentration, whereas water vapor addition decreased NO_x emission in CH₄ combustion over the Sr_0.8La_0.2MnAl₁₁O₁₉₋ catalyst. In the catalytic combustion of C₃H₈ over the Sr_0.8La_0.2MnAl₁₁O₁₉₋ catalyst, the amount of NO_x emitted was raised in the temperature range between 1000 and 1500 °C when the C₃H₈ concentration increased from 1 to 2 vol.%. It was found that NO_x emission in this temperature range was reduced effectively by adding water vapor.     

Activity and stability of Ag–alumina for the selective catalytic reduction of NOx with methane in high-content SO2 gas streams

In this work, we investigated the activity and stability of Ag–alumina catalysts for the SCR of NO with methane in gas streams with a high concentration of SO₂, typical of coal-fired power plant flue gases. Ag–alumina catalysts were prepared by coprecipitation–gelation, and dilute nitric-acid solutions were used to remove weakly bound silver species from the surface of the as prepared catalysts after calcination. SO₂ has a severe inhibitory effect, essentially quenching the CH₄-SCR reaction on this type catalysts at temperatures <600 °C. SO₂ adsorbs strongly on the surface forming aluminum and silver sulfates that are not active for CH₄-SCR of NO_x. Above 600 °C, however, the reaction takes place without catalyst deactivation even in the presence of 1000 ppm SO₂. The reaction light-off coincides with the onset of silver sulfate decomposition, indicating the critical role of silver in the reaction mechanism. SO₂ is reversibly adsorbed on silver above 600 °C. While alumina sites remain sulfated, this does not hinder the reaction. Sulfation of alumina only decreases the extent of adsoption of NO_x, but adsorption of NO_x is not the limiting step. Methane activation is the limiting step, hence the presence of sulfur-free Ag–O–Al species is a requirement for the reaction. Strong adsorption of SO₂ on Ag–alumina decreases the rates of the reaction, and increases the activation energies of both the reduction of NO to N₂ and the oxidation of CH₄, the latter more than the former. Our results indicate partial contribution of gas phase reactions to the formation of N₂ above 600 °C. H₂O does not inhibit the reaction at 625 °C, and the effect of co-addition of H₂O and SO₂ is totally reversible.     

Zeolite-mediated removal of NOx by NH3 from exhaust streams at low temperatures

NH₃ stored on zeolites in the form of NH₄⁺ ions easily reacts with NO to N₂ in the presence of O₂ at temperatures <373 K under dry conditions. Wet conditions require a modification of the catalyst system. It is shown that MnO₂ deposited on the external surface of zeolite Y by precipitation considerably enhances the NO_x conversion by zeolite fixed NH₄⁺ ions in the presence of water at 400–430 K. Particle-size analysis, temperature-programmed reduction, textural characterization, chemical analysis, ESR and XRD gave a subtle picture of the MnO₂ phase structure. The MnO₂ is a non-stoichiometric, amorphous phase that contains minor amounts of Mn²⁺ ions. It loses O₂ upon inert heating up to 873 K, but does not crystallize or sinter. The phase is reducible by H₂ in two stages via intermediate formation of Mn₃O₄. The manufacture of extrudates preserving stored NH₄⁺ ions for NO_x reduction is described. It was found that MnO₂ can oxidize NO by bulk oxygen. This enables the reduction of NO to N₂ by the zeolitic NH₄⁺ ions without gas-phase oxygen for limited time periods. The composite catalyst retains storage capacity for both, oxygen and NH₄⁺ ions despite the presence of moisture and allows short-term reduction of NO without gaseous O₂ or additional reductants. The catalyst is likewise suitable for steady-state DeNO_x operation at higher space velocities if gaseous NH₃ is permanently supplied.     

The removal of NOx from a lean exhaust gas using storage and reduction on H3PW12O40·6H2O

NO_x sorption and reduction capacities of 12-tungstophosphoric acid hexahydrate (H₃PW₁₂O₄₀·6H₂O, HPW) were measured under representative alternating conditions of lean and rich exhaust-type gas mixture. Under lean conditions, the sorption of NO_x is large and is equivalent to 37 mg of NO_x/g_HPW. Although a part of these NO_x remains unreduced, HPW is able to reduce some of the NO_x to produce N₂ by a reaction between the sorbed NO₂ and hydrocarbon (HC), but this process is slow. The addition of 1% Pt affects strongly the chemical behaviour occurring during the course of a rich operation. The NO desorption observed at the beginning of the rich phase is strongly accelerated. The direct correlation between NO₂ consumption and CO₂ production shows that the principal pathway is the reaction CO+NO₂→CO₂+NO. In a mixture of reducing gas (CO, HC, H₂), the competition is strongly in favour of CO though in its absence the reaction observed was the hydrogenation of propene to propane.     

Analysis of the thermodynamic feasibility of NOx decomposition catalysis to meet next generation vehicle NOx emissions standards

Free energy minimization calculations are used to determine the thermodynamic equilibrium concentrations of NO_x and other species in stoichiometric and lean gas mixtures over a range of temperatures and compositions. Under lean (excess N₂ and O₂) conditions, the NO decomposition (NO↔(1/2)N₂+(1/2)O₂) and NO oxidation (NO+(1/2)O₂↔NO₂) equilibria impose lower bounds on the NO_x concentrations achievable by thermodynamic equilibration or NO_x decomposition, and these equilibrium NO_x concentrations can be practically significant. Assuming a perfect isothermal catalyst acting on a representative diesel exhaust stream collected over the federal test procedure (FTP) cycle, equilibrium NO_x levels exceed upcoming California Low Emission Vehicle II (LEV-II) and Tier II NO_x emissions standards for automobiles and trucks at temperatures above approximately 800 K. Consideration of a perfect adiabatic catalyst acting on the same diesel exhaust shows that equilibrium NO_x values can fall below NO_x emissions standards at lower temperatures, but to achieve these low concentrations would require the catalyst to attain 100% approach to equilibrium at very low temperatures. It is concluded that NO_x removal based on a thermodynamic equilibrating catalyst under lean exhaust conditions is not practically viable for automotive application, and that to achieve upcoming NO_x standards will require selective NO_x catalysts that vigorously promote NO_x reactions with reductant and do not promote NO decomposition or oxidation. Finally, the ability of a selective NO_x catalyst system to reduce NO_x concentrations to or below thermodynamic equilibrium values is proposed as a useful measure for selective catalytic reduction (SCR) activity.     

Transient analysis of the release and reduction of NOx using a Pt/Ba/Al2O3 catalyst

The release and reduction of NO_x in a NO_x storage-reduction (NSR) catalyst were studied with a transient reaction analysis in the millisecond range, which was made possible by the combination of pulsed injection of gases and time resolved time-of-flight mass spectrometry. After an O₂ pulse and a subsequent NO pulse were injected into a pellet of the Pt/Ba/Al₂O₃ catalyst, the time profiles of several gas products, NO, N₂, NH₃ and H₂O, were obtained as a result of the release and reduction of NO_x caused by H₂ injection. Comparing the time profiles in another analysis, which were obtained using a model catalyst consisting of a flat 5 nmPt/Ba(NO₃)₂/cordierite plate, the release and reduction of NO_x on Pt/Ba/Al₂O₃ catalyst that stored NO_x took the following two steps; in the first step NO molecules were released from Ba and in the second step the released NO was reduced into N₂ by H₂ pulse injection. When this H₂ pulse was injected in a large amount, NO was reduced to NH₃ instead of N₂.

A only small amount of H₂O was detected because of the strong affinity for alumina support. We can analyze the NO_x regeneration process to separate two steps of the NO_x release and reduction by a detailed analysis of the time profiles using a two-step reaction model. From the result of the analysis, it is found that the rate constant for NO_x release increased as temperature increase.     

CO2, NOx and SO2 emissions from the combustion of coal with high oxygen concentration gases

The emissions of CO₂, NO_x and SO₂ from the combustion of a high-volatile coal with N₂- and CO₂-based, high O₂ concentration (20, 50, 80, 100%) inlet gases were investigated in an electrically heated up-flow-tube furnace at elevated gas temperatures (1123–1573 K). The fuel equivalence ratio, φ, was varied in the range of 0.4–1.6. Results showed that CO₂ concentrations in flue gas were higher than 95% for the processes with O₂ and CO₂-based inlet gases. NO_x emissions increased with φ under fuel-lean conditions, then declined dramatically after φ=0.8, and the peak values increased from about 1000 ppm for the air combustion process and 500 ppm for the O₂(20%)+CO₂(80%) inlet gas process to about 4500 ppm for the oxygen combustion process. When φ>1.4 the emissions decreased to the same level for different O₂ concentration inlet gas processes. On the other hand, NO_x emission indexes decreased monotonically with φ under both fuel-lean and fuel-rich combustion. SO₂ emissions increased with φ under fuel-lean conditions, then declined slightly after φ>1.2. Temperature has a large effect on the NO_x emission. Peak values of the NO_x emission increased by 50–70% for the N₂-based inlet gas processes and by 30–50% for the CO₂-based inlet gas process from 1123 to 1573 K. However, there was only a small effect of temperature on the SO₂ emission.     

Impact of redox conditions on thermal deactivation of NOx traps for diesel

Performance of NO_x traps after high-temperature treatments in different redox environments was studied. Two types of treatments were considered: aging and pretreatment. Lean and rich agings were examined for a model NO_x trap, Pt–Ba/Al₂O₃. These were done at 950 °C for 3 h, in air and in 1% H₂/N₂, respectively. Lean aging had a severe impact on NO_x trap performance, including HC and CO oxidation, and NH₃ and N₂O formation. Rich aging had minimal impact on performance, compared to fresh/degreened performance. Deactivation from lean aging was essentially irreversible due to Pt sintering, but Pt remained dispersed with the rich aging. Pretreatments were examined for a commercially feasible fully formulated NO_x trap and two model NO_x traps, Pt–Ba/Al₂O₃ and Pt–Ba–Ce/Al₂O₃. Pretreatments were done at 600 °C for 10 min, and used feed gas that simulated diesel exhaust under several conditions. Lean pretreatment severely suppressed NO_x, HC, CO, NH₃ and N₂O activities for the ceria-containing NO_x traps, but had no impact on Pt–Ba/Al₂O₃. Subsequently, a relatively mild rich pretreatment reversed this deactivation, which appears to be due to a form of Pt–ceria interaction, an effect that is well known from early work on three-way catalysts. Practical applications of results of this work are discussed with respect to NO_x traps for light-duty diesel vehicles.     

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.     

Transient behaviour of catalytic monolith with NOx storage capacity

Transient behaviour of catalytic monolith converter with NO_x storage is studied under conditions typical for automobiles with lean-burn engines (i.e., diesel and advanced gasoline ones). Periodical alternation of inlet concentrations is applied—NO_x are adsorbed on the catalyst surface during a long reductant-lean phase (2–3 min) and then reduced to N₂ within a short reductant-rich phase (2–6 s). Samples of industrial NO_x storage and reduction catalyst of NM/Ba/CeO₂/γ-Al₂O₃ type (NM = noble metal), washcoated on 400 cpsi cordierite substrate, are used in the study. Effects of the rich-phase length and composition on the overall NO_x conversions are examined experimentally. Reduction of NO_x by CO, H₂ and unburned hydrocarbons (represented by C₃H₆) in the presence of CO₂ and H₂O is considered.

Effective, spatially 1D, heterogeneous mathematical model of catalytic monolith with NO_x and oxygen storage capacity is described. The minimum set of experiments needed for the evaluation of relevant reaction kinetic parameters is discussed: (i) CO, H₂ and HC oxidation light-off under both lean and rich conditions, including inhibition effects, (ii) NO/NO₂ transformation, (iii) NO_x storage, including temperature dependence of effective NO_x storage capacity, (iv) water gas shift and steam reforming under rich conditions, i.e., in situ production of hydrogen, (v) oxygen storage and reduction, including temperature dependence of effective oxygen storage capacity, and (vi) NO_x desorption and reduction under rich conditions. The experimental data are compared with the simulation results.