Influence of CO2 on storage and release of NOx on barium‐containing catalyst

A barium‐containing three‐way automotive emission catalyst was submitted to a NO_x storage step in flowing lean gas mixture containing 340 ppm NO and 8 vol% O₂ in helium. NO_x release was carried out in the 250–550°C temperature range, either in pure helium or in the presence of a 10 vol% CO₂ in helium mixture. It was shown that at 450–550°C all of the stored NO_x on the barium trap can be released fastly in the CO₂‐containing gas mixture or, after a longer time, in pure helium: these data show that NO_x release can occur in the absence of a reducing agent. The NO_x release was not complete at 350°C and did not occur at 250°C. The assisting effect of CO₂ as regards to NO_x release was interpreted in terms of the existence of the CO_2,gas + *NO_2,stored ⇌ *CO_2,stored + NO_2,gas equilibrium, suggesting the competitive storage of CO₂ and NO₂ for a unique type of barium storage sites (*). This revised version was published online in July 2006 with corrections to the Cover Date.     

NOx storage on barium-containing three-way catalyst in the presence of CO2

NO_x trapping capability of NO_x storage–reduction commercial catalysts (4–9 wt% Ba-containing three-way catalysts) was compared to that of bulk barium carbonate and alumina-supported barium carbonate from Rhodia (9 wt% Ba). These samples were characterized by infrared spectroscopy, X-ray diffraction, HRTEM and EDX. It was shown that bulk barium carbonate was partially converted to barium nitrate in flowing NO/O₂ mixture without CO₂. Thermodynamic calculation showed that bulk barium nitrate could not form in the presence of CO₂-containing gas exhausts. Using HRTEM and EDX, it was evidenced that barium was engaged as either large barium carbonate crystals or highly dispersed barium species on the alumina support. NO_x storage experiments using gas mixtures containing or not O₂ or CO₂, confirmed firstly that NO was stored on barium trap only via NO₂ and secondly that NO₂ and CO₂ are competing for the same barium trapping sites. The fact that no significant amount of stored NO_x could be evidenced in the bulk barium carbonate, suggested that over the catalytic surface, the well dispersed barium phase can play an important role in the NO_x trapping properties of these catalysts.     

Fundamental studies of NOx storage at low temperatures

A commercial NO_x storage catalyst (Pt, BaO and alumina containing) was investigated by temperature programmed desorption (TPD) experiments in the temperature range 100–400 °C. The catalyst stored a substantial amount of NO_x at 100 °C using NO + O₂. Nitrites or loosely bound NO species are suggested for this storage, since no NO was oxidised at this low temperature. In addition, the released NO_x during the temperature ramp consisted of mainly NO and at lower temperatures the NO₂ dissociation is limited. Water and CO₂ was found to decrease the storage substantially, 92% for the NO + O₂ adsorption at 100 °C. The total storage for 60 min using NO₂ + O₂ at 200 °C was similar when introducing CO₂ and H₂O. However, the initial total uptake of NO_x was decreased. Initially we probably formed loosely bound NO_x species, which likely are strongly influenced by water and CO₂. After longer time periods are barium nitrates probably formed and they can remove the carbonates by forming stable nitrates, thus resulting in the same total uptake of NO_x.     

Model Studies of NOx Storage and Sulphur Deactivation of NOx Storage Catalysts

The storage of NO _x under lean conditions in model NO _x storage catalysts as well as the deactivation by sulphur have been studied. We find that NO₂ plays an important role in the storage mechanism as an oxidising agent. Two different mechanisms for this are discussed: the formation of surface peroxides and the oxidation of nitrites to nitrates. FTIR studies show that NO _x is stored as surface nitrates. The sulphur deactivation is found to be more severe when SO₂ is added during the rich phase than when SO₂ is added during the lean period. FTIR shows the formation of bulk sulphates both under lean and rich conditions.     

Influence of the Storage Material on the Storage of NOx at Low Temperatures

The NO _x storage performance at low temperature (100–200 °C) has been studied for model NO _x storage catalysts. The catalysts were prepared by sequentially depositing support, metal oxide and platinum on ceramic monoliths. The support material consisted of acidic aluminium silicate, alumina or basic aluminium magnesium oxide, and the added metal oxide was either ceria or barium oxide. The NO _x conversion was evaluated under net-oxidising conditions with transients between lean and rich gas composition and the NO _x storage performance was studied by isothermal adsorption of NO₂ followed by temperature programmed desorption of adsorbed species. The maximum in NO _x storage capacity was observed at 100 °C for all samples studied. The Pt/BaO/Al₂O₃ catalyst stored about twice the amount of NO _x compared with the Pt/Al₂O₃ and Pt/CeO₂/Al₂O₃ samples. The storage capacity increased with increasing basicity of the support material, i.e. Pt/Al₂O₃·SiO₂ < Pt/Al₂O₃ < Pt/Al₂O₃ · MgO. Water did not significantly affect the NO _x storage performance for Pt/Al₂O₃ or Pt/BaO/Al₂O₃.     

The role of acid sites in cobalt zeolite catalysts for selective catalytic reduction of NOx

The role of the acidic support in ion-exchanged cobalt-zeolite, lean NO_x catalysts has been determined by studying the individual steps in the selective reduction pathway. At a GHSV of 10,000 and reaction temperatures below 400°C, NO oxidation is not sufficiently rapid to obtain equilibrium over, for example, 1–4 wt% Co-mordenite catalysts. The NO oxidation rate increases in the order H⁺Co²⁺ Co oxide, and neither the number, nor the strength of the acid sites affects the specific rate of the Co²⁺ ions. For reduction of NO₂ by propylene at 300°C and methane at 400°C, the formation of N₂ is suggested to occur at support protons sites. In addition, the rate of N₂ formation increases linearly with an increase in the number of acid sites, and the specific activity increases with an increase in acid strength. Cobalt (2+) ions do not contribute significantly to the formation of N₂, but do non-selectively reduce NO₂ to NO. It is proposed that the formation of N₂ occurs by protonation of the reducing agent followed by attack of the carbocation by gas phase NO₂. Thus, the selective reduction of NO requires two catalytic functions, metal and acid sites. This revised version was published online in July 2006 with corrections to the Cover Date.     

The Effect of Carbon Monoxide and Hydrocarbons on NOx Storage at Low Temperature

One possible way to reduce NO _x in lean exhausts is by using NO _x trap catalysts. This paper addresses storage of NO _x on such catalysts at temperatures below the catalyst light-off. Experiments carried out on commercial samples in synthetic exhausts revealed a large capacity for storage of NO _x when NO₂ was added at temperatures below 150°C. In contrast, when NO was added instead, no storage took place. CO was found to decrease the storage by reacting with NO₂ and forming NO and CO₂. Propene inhibited the reaction between NO₂ and CO and therefore gave rise to larger NO _x storage when CO was present. The paper concludes with a discussion of a possible mechanism for the storage of NO _x at low temperatures.     

CO2 effect on activity and stability of NOx storage reduction catalysts

A catalyst for NO_x storage/reduction was prepared to improve the activity of Ba–Pt/γ-Al₂O₃ by replacing Ba with a mixture of Ba and Mg. The catalyst was prepared by impregnating Pt and then co-impregnating Ba and Mg (Mg:Ba molar ratio = 1) on commercial γ-Al₂O₃. The tests have been carried out in the presence of CO₂ at temperatures between 200 and 400 °C in order to understand the role of both the feed and various alkaline-earth metals. The storage capacity of the two catalysts was different like the mechanism in the reduction process.     

An Investigation of Catalysts for the On Board Synthesis of NH3. A Possible Route to Low Temperature NOx Reduction for Lean-Burn Engines

Platinum group metal catalysts have been investigated for the formation of NH₃ from NO + H₂ at low temperatures in the absence and presence of CO. Although CO inhibits the formation of NH₃, substantial amounts are still observed with a Pt catalyst. By combining Pt with a support (ceria–zirconia) that has low temperature NO_x storage characteristics it has been shown in transient experiments that NH₃ can be formed and stored in situ under rich conditions, and may then be used to reduce NO_x under lean burn conditions.     

Supported Heteropolyacids for NOx Storage and Reduction

TiO₂ and SnO₂ were studied as possible supports for HPW in order to produce a new type of sorbent for NO _x trap applications. SnO₂ was synthesised by various inorganic methods while TiO₂ was purchased commercially. The sorption capacities and efficiencies depend upon the BET surfaces. Best performances were obtained with support with large pores where the crystalline structure of HPW is maintained. The optimal loading of HPW is ca. 50% with BET surface in the range 20–80 m²g^–1.     

NOx Storage-Reduction Three-Way Catalyst with Improved Sulfur Tolerance

The NO _x storage-reduction catalyst (NSR catalyst) is poisoned by SO₂ caused by fuel sulfur, thus its activity is reduced. In order to improve the NSR catalyst, the sulfur poisoning phenomenon has been analyzed. Based on this result, we developed TiO₂ and Rh/ZrO₂ to promote the sulfur desorption. The developed catalyst has made remarkable progress in its sulfur tolerance, about 50% improvement in NO _x purification performance compared with the conventional one.     

Reduction of NOx over a NOx-Trap Catalyst and the Regeneration Behaviour of Adsorbed SO2

A conventional NO _x -trap catalyst containing platinum, rhodium, barium and lanthanum was conditioned with oxygen at 500°C, preloaded with NO under standard oxidising conditions and then subjected to regeneration with the reductants H₂, CO and C₃H₆, either alone or as a mixture. Hydrogen is the most efficient reductant in terms of NO _x conversion efficiency and reductant usage efficiency. There is a temperature optimum for CO between 300 and 400°C and a catalyst loading optimum (mols reductant added)/(mols NO _x adsorbed) between 1.5 and 3.0. The behaviour of the catalyst towards sulphur poisoning was examined in supplementary trials with the adsorption of SO₂ in the presence or absence of water vapour. When water is not present in both adsorption and reduction steps, very stable sulphates are formed, unattacked by reductants even at 1000°C. Sulfates are more easily reduced when water is present in the reductant mixture.     

Fundamental Investigations of Thermal Aging Phenomena of Model NOx Storage Systems

Investigations of the aging behavior induced by high temperatures coupled with oxidizing atmosphere of model NO _x storage systems Ba/Al₂O₃ and Ba/CeO₂ are reported in this paper. The samples were prepared, calcined and exposed to temperatures between 500 and 1000 °C in air for 12 h for thermal aging. Samples were characterized with XRD, HRSEM, DSC-TGA-MS and BET analyses. In XRD investigations of all model systems calcined at 500 °C for 2 h, the NO _x storage component was present in form of BaCO₃. The release of CO₂ as a result of the decarbonization of the NO _x storage component at increased temperatures was verified by thermogravimetric investigations. In the case of Ba/Al₂O₃, already during calcination a partial reaction of the NO _x storage component with Al₂O₃ resulting in the formation of barium aluminate was observed. In the model system Ba/CeO₂ the decomposition of the barium carbonate started above 780 °C and the formation of a barium cerium mixed oxide was observed. The presence of the barium containing NO _x storage component has a strong influence on the specific surface area of the model NO _x storage systems. The morphology and crystallite size of CeO₂ modified with the barium containing NO _x storage component exhibited distinct changes compared to the unmodified oxide. The NO _x storage efficiency determined by model gas tests of freshly prepared and engine aged model NO _x storage catalysts correlates well with the above described observations.     

Platinum Oxidation and Sulphur Deactivation in NOx Storage Catalysts

Flow reactor experiments and X-ray photoelectron spectroscopy (XPS) measurements were used to investigate the importance of platinum oxide formation on Pt/BaO/Al₂O₃ NO _x storage catalysts during reactions conditions. The reaction studied was NO(g) + 1/2 O₂(g) NO₂(g). During NO₂ exposure of the catalyst the NO₂ dissociation rate decreased during the reaction. This activity decrease with time was also studied with XPS and it was found to be due to platinum oxide formation. The influence of sulphur exposure conditions on the performance of the NO _x storage catalysts was studied by exposing the samples to lean and/or rich gas mixtures, simulating the conditions in a mixed lean application, containing SO₂. The main results show that all samples are sensitive to sulphur and that the deactivation proceeds faster when SO₂ is present in the feed under rich conditions than under lean or continuous SO₂ exposure. Additionally, the influence of the noble metals present in the catalysts was investigated regarding sulphur sensitivity and it was found that a combination of platinum and rhodium seems to be preferable to retain high performance of the catalyst under SO₂ exposure and subsequent regeneration. Finally, the behaviour of micro-fabricated model NO _x storage catalysts was studied as a function of temperature and gas composition with area-resolved XPS. These model catalysts consisted of a thin film of Pt deposited on one-half of a BaCO₃ pellet. It was found that the combination of SO₂ and O₂ resulted in migration of Pt on the BaCO₃ support up to one mm away from the Pt/BaCO₃ interface.     

Sorption–Desorption of NOx from a Lean Gas Mixture on H3PW12O40·6H2O Supported on Carbon Nanotubes

NO _x sorption capacities and efficiencies were measured on a new type of sorbent formed by 12-tungstophosphoric acid (HPW) supported on carbon nanotubes. On such a system, the sorption of both NO and NO₂ was observed but compared with HPW alone, a complementary sorption of NO _x is possible leading to a capacity of 25 mg/g_HPW at 300 °C with an efficiency of 50%. The sorption results from the formation of a [H⁺(NO₂ ^–,NO⁺)] complex on HPW and an additional mode of adsorption by a free-nitrate which was identified by the bands at 2261, 1384 and 1295 cm^–1 using infrared spectroscopy.     

Effects of Lean/Rich Timing and Nature of Reductant on the Performance of a NOx Trap Catalyst

A NO _x trap catalyst was studied in a laboratory reactor under simulated diesel passenger car conditions. The effects of lean/rich duration and the nature of reductant are investigated. At 300°C, the average NO _x conversion decreases with increasing lean duration; conversely the NO _x conversion increases with increasing rich duration. The NO _x conversion at this temperature was found to be a direct function of reaction stoichiometry. That is, the quantity of trapped NO _x under lean conditions must be balanced by the quantity of reductant during the rich trap regeneration step. At extreme temperatures, other factors, reaction kinetics (at lower temperatures) and NO _x storage capacity (at higher temperatures), dominate the NO _x conversion process. Overall, carbon monoxide was found to be the most effective reductant. Hydrocarbon, e.g., C₃H₆, is effective at higher temperatures (T>350°C), while H₂ is more efficient than other reductants at low temperatures (T<200°C). The individual steps of the NO _x conversion process are discussed.     

Spectroscopic Evidence for a Nitrite Intermediate in the Catalytic Reduction of NOx with Ammonia on Fe/MFI

The mechanism of selective catalytic reduction (SCR) of NO_x with NH₃ over Fe/MFI was studied using in situ FTIR spectroscopy. Exposing Fe/MFI first to NH₃ then to flowing NO + O₂ or using the reversed sequence, invariably leads to the formation of ammonium nitrite, NH₄NO₂. In situ FTIR results in flowing NO + NH₃ + O₂ at different temperatures show that NH₃ is strongly adsorbed and reacts with impinging NO_x. The intensity of the NH₄NO₂ bands initially increases with temperature, but passes through a maximum at 120 °C because the nitrite decomposes to N₂ + H₂O. The mechanistic model rationalizes that the consumption ratio of NO and NH₃ is close to unity and that the effect of water vapor depends on the reaction temperature. At high temperature H_2O enhances the rate because it is needed to form NH₄NO₂. At low temperature, when adsorbed H₂O is abundant it lowers the rate because it competes with NO_x for adsorption sites.     

Deterioration Mode of Barium-Containing NOx Storage Catalyst

Barium-containing NO _x storage catalyst showed serious deactivation under thermal exposure at high temperatures. To elucidate the thermal deterioration of the NO _x storage catalyst, four types of model catalyst, Pt/Al₂O₃, Ba/Al₂O₃, Pt–Ba/Al₂O₃, and a physical mixture of Pt/Al₂O₃ + Ba/Al₂O₃ were prepared and their physicochemical properties such as BET, NO TPD, TGA/DSC, XRD, and XPS were evaluated while the thermal aging temperature was increased from 550 to 1050°C. The fresh Pt–Ba/Al₂O₃ showed a sorption capacity of 3.35 wt%/g-cat. but the aged one revealed a reduced capacity of 2.28 wt%/g-cat. corresponding to 68% of the fresh one. It was found that this reduced sorption capacity was directly related to the deterioration of the NO _x storage catalyst by thermal aging. The Ba on Ba/Al₂O₃ and Pt–Ba/Al₂O₃ catalysts began to interact with alumina to form Ba–Al solid alloy above 600°C and then transformed into stable BaAl₂O₄ having a spinel structure. However, no phase transition was observed in the Pt/Al₂O₃ catalyst having no barium component, even after aging at 1050°C.     

Transient Surface Processes of Storage and Conversion of NOx Species on Pt–Me/Al2O3 Catalysts (Me = Ba,Ce, Cu)

The transient reactivity and surface phenomena of storage and conversion of NO _x species on Pt(1%)–Me/Al₂O₃ catalysts, where Me = Ba, Ce and Cu, were studied by the RWF (rectangular wavefront) method. The Me component has a relevant influence on the processes of surface storage and transformation. The reduction of NO _x by propene in the presence of oxygen is promoted by adding Cu to a Pt/Al₂O₃ catalyst, while cerium promotes transient conversion of NO in the absence of propene, but inhibits the reduction of NO _x in the presence of propene. Copper is suggested to be a promising element to add together with Ba for new NO _x storage-reduction catalysts due to its capacity to act both as a storage element and as promoter for NO _x reduction.     

NOx Storage and Reduction Catalysts for Automotive Lean-Burn Engines: Effect of Parameters and Storage Materials on NOx Conversion

The effect of various parameters on the NO _x conversion over NO _x storage and reduction catalysts supported on alumina was investigated. The Pt/BaO/Al₂O₃ catalyst exhibited a higher NO _x reduction activity than the Pt/Al₂O₃ catalyst under the static and cycling conditions. The activity of Pt/BaO/Al₂O₃ catalyst was improved in the cycled feedstream. The Pt/SrO/Al₂O₃ was found to have as high activity as Pt/BaO/Al₂O₃ for NO _x reduction. In order to achieve effective reduction of NO _x , NO _x storage in the form of Me(NO₃)₂ (Me = Ba or Sr) is more favorable than other nitrates and the rich condition should be chosen in such a way that the sorption capacity can be fully regenerated at a fast rate and the inhibition effect by strongly adsorbed molecules derived from C₃H₆ and CO can be minimized.