Measures to Reduce the N2O Formation at Perovskite-Based Lean NOx Trap Catalysts under Lean Conditions

The net oxidising atmosphere of lean burn engines requires a special after-treatment catalyst for NOx removal from the exhaust gas. Lean NOx traps (LNT) are such kind of catalysts. To increase the efficiency of LNTs at low temperatures platinised perovskite-based infiltration composites La0.5Sr0.5Fe1-xMxO3-δ/Al2O3 with M = Nb, Ti, Zr have been developed. In general, platinum based LNT catalysts show an undesired, hazardous formation of N2O in the lean operation mode due to a competing C3H6-selective catalytic reduction (SCR) at the platinum sites. To reduce N2O emissions an additional Rh-coating, obtained by incipient wetness impregnation, besides the Pt coating and a two-layered oxidation catalyst (2 wt.% Pd/20 wt.% CeO2/alumina)-LNT constitution, has been investigated. Though the combined Rh-Pt coating shows a slightly increased NOx storage capacity (NSC) at temperatures above 300 °C, it does not decrease N2O formation. The layered oxidation catalyst-LNT system shows a decrease in N2O formation of up to 60% at 200 °C, increasing the maximum NSC up to 176 µmol/g. Furthermore, the NSC temperature range is broadened compared to that of the pure LNT catalyst, now covering a range of 250–300 °C.

Perovskite-Based Catalysts as Efficient, Durable, and Economical NOx Storage and Reduction Systems

Diesel engines operate under net oxidizing environment favoring lower fuel consumption and CO2 emissions than stoichiometric gasoline engines. However, NOx reduction and soot removal is still a technological challenge under such oxygen-rich conditions. Currently, NOx storage and reduction (NSR), also known as lean NOx trap (LNT), selective catalytic reduction (SCR), and hybrid NSR–SCR technologies are considered the most efficient control after treatment systems to remove NOx emission in diesel engines. However, NSR formulation requires high platinum group metals (PGMs) loads to achieve high NOx removal efficiency. This requisite increases the cost and reduces the hydrothermal stability of the catalyst. Recently, perovskites-type oxides (ABO3) have gained special attention as an efficient, economical, and thermally more stable alternative to PGM-based formulations in heterogeneous catalysis. Herein, this paper overviews the potential of perovskite-based formulations to reduce NOx from diesel engine exhaust gases throughout single-NSR and combined NSR–SCR technologies. In detail, the effect of the synthesis method and chemical composition over NO-to-NO2 conversion, NOx storage capacity, and NOx reduction efficiency is addressed. Furthermore, the NOx removal efficiency of optimal developed formulations is compared with respect to the current NSR model catalyst (1–1.5 wt % Pt–10–15 wt % BaO/Al2O3) in the absence and presence of SO2 and H2O in the feed stream, as occurs in the real automotive application. Main conclusions are finally summarized and future challenges highlighted.

High Performance of Mn-Doped MgAlOx Mixed Oxides for Low Temperature NOx Storage and Release

NOx storage-reduction (NSR) is a potential approach for the effective removal of NOx under the lean conditions in lean-burn engines. Herein, manganese-doped mixed oxides (Mn/MgAlOx) with high performance for low temperature NOx storage and release were derived from hydrotalcites precursors prepared by a facile coprecipitation method. The catalysts were characterized by X-ray diffraction (XRD), SEM, N2 adsorption-desorption, H2-TPR, FT-IR, and X-ray photoelectron spectroscopy (XPS) techniques. The Mn-doped MgAlOx catalysts exhibited high NOx storage capacity (NSC) at low temperature range (150–300 °C), which was related to their increased surface area, improved reducibility and higher surface Mn3+ content. The largest NSC measured, 426 μmol/g, was observed for NOx adsorption at 200 °C on Mn15 catalyst (the sample containing 15 wt% of Mn). The in situ DRIFTS spectra of NOx adsorption proved that the Mn-doped hydrotalcite catalysts are preferred for low temperature NOx storage and release due to their ability to store NOx mainly in the form of thermally labile nitrites. NSR cycling tests revealed the NOx removal rate of Mn15 sample can reach above 70% within the wide temperature range of 150–250 °C. Besides, the influence of CO2, soot, H2O and SO2 on NOx storage performance of Mn15 catalyst was also studied. In all, owning to their excellent NOx storage capacity, NSR cycling performance, and resistance to CO2, soot, SO2 and H2O, the Mn-doped MgAlOx NSR catalysts have broad application prospects in NOx control at low temperatures.

Improved NOx Storage/Release Properties of Ceria-Based Lean NOx Trap Compositions with MnOx Modification

Ceria/spinel-based lean NOx trap compositions with and without barium were modified with MnOx via incipient wetness impregnation. The effect of the MnOx layer on the aged materials (850 °C) as to the NOx storage and release properties was investigated via NOx adsorption (500 ppm NO/5% O2/balance N2) carried out at 300 °C in a dual-bed with a 1% Pt/Al2O3 catalyst placed upstream of the samples to generate sufficient amounts of NO2 required for efficient NOx storage. Subsequent temperature programmed desorption (TPD) experiments were carried out under N2 from 300 °C to 700 °C. The addition of MnOx to the barium free composition led to a slightly reduced NOx storage capacity but all of the ad-NOx species were released from this material at significantly lower temperatures (ΔT ≈ 100 °C). The formation of a MnOx layer between ceria/spinel and barium had a remarkable effect on ageing stability as the formation of BaAl2O4 was suppressed in favour of BaMnO3. The presence of this phase resulted in an increased NOx storage capacity and lower desorption temperatures. Furthermore, NOx adsorption experiments carried out in absence of the Pt-catalyst also revealed an unexpected high NOx storage ability at low NO2/NO ratios, which could make this composition suitable for various lean NOx trap catalysts (LNT) related applications.

BaTi0.8B0.2O3 (B = Mn, Fe, Co, Cu) LNT Catalysts: Effect of Partial Ti Substitution on NOx Storage Capacity

The effect of partial Ti substitution by Mn, Fe, Co, or Cu on the NOx storage capacity (NSC) of a BaTi0.8B0.2O3 lean NOx trap (LNT) catalyst has been analyzed. The BaTi0.8B0.2O3 catalysts were prepared using the Pechini’s sol–gel method for aqueous media. The characterization of the catalysts (BET, ICP-OES, XRD and XPS) reveals that: i) the partial substitution of Ti by Mn, Co, or Fe changes the perovskite structure from tetragonal to cubic, whilst Cu distorts the raw tetragonal structure and promotes the segregation of Ba2TiO4 (which is an active phase for NOx storage) as a minority phase and ii) the amount of oxygen vacancies increases after partial Ti substitution, with the BaTi0.8Cu0.2O3 catalyst featuring the largest amount. The BaTi0.8Cu0.2O3 catalyst shows the highest NSC at 400 °C, based on NOx storage cyclic tests, which is within the range of highly active noble metal-based catalysts.

Investigation of Various Pd Species in Pd/BEA for Cold Start Application

A series of Pd/BEA catalysts with various Pd loadings were synthesized. Two active Pd2+ species, Z−-Pd2+-Z− and Z−-Pd(OH)+, on exchanged sites of zeolites, were identified by in situ FTIR using CO and NH3 respectively. Higher NOx storage capacity of Z−-Pd2+-Z− was demonstrated compared with that of Z−-Pd(OH)+, which was caused by the different resistance to H2O. Besides, lower Pd loading led to a sharp decline of Z−-Pd(OH)+, which was attributed to the ‘exchange preference’ for Z−-Pd2+-Z− in BEA. Based on this research, the atom utilization of Pd can be improved by decreasing Pd loading.

Gas-Phase Phosphorous Poisoning of a Pt/Ba/Al2O3 NOx Storage Catalyst

The effect of phosphorous exposure on the NOx storage capacity of a Pt/Ba/Al2O3 catalyst coated on a ceramic monolith substrate has been studied. The catalyst was exposed to phosphorous by evaporating phosphoric acid in presence of H2O and O2. The NOx storage capacity was measured before and after the phosphorus exposure and a significant loss of the NOx storage capacity was detected after phosphorous exposure. The phosphorous poisoned samples were characterized by X-ray photoelectron spectroscopy (XPS), environmental scanning electron microscopy (ESEM), N2-physisorption and inductive coupled plasma atomic emission spectroscopy (ICP-AES). All characterization methods showed an axial distribution of phosphorous ranging from the inlet to the outlet of the coated monolith samples with a higher concentration at the inlet of the samples. Elemental analysis, using ICP-AES, confirmed this distribution of phosphorous on the catalyst surface. The specific surface area and pore volume were significantly lower at the inlet section of the monolith where the phosphorous concentration was higher, and higher at the outlet where the phosphorous concentration was lower. The results from the XPS and scanning electron microscopy (SEM)-energy dispersive X-ray (EDX) analyses showed higher accumulation of phosphorus towards the surface of the catalyst at the inlet of the monolith and the phosphorus was to a large extent present in the form of P4O10. However, in the middle section of the monolith, the XPS analysis revealed the presence of more metaphosphate (PO3−). Moreover, the SEM-EDX analysis showed that the phosphorous to higher extent had diffused into the washcoat and was less accumulated at the surface close to the outlet of the sample.

Storage of Nitrous Oxide (NOx) in Diesel Engine Exhaust Gas using Alumina-Based Catalysts: Preparation, Characterization, and Testing

This work investigated the nitrous oxide (NOx) storage process using alumina-based catalysts (K2 O/Al2 O3 , CaO/Al2 O3, and BaO/Al2 O3 ). The feed was a synthetic exhaust gas containing 1,000 ppm of nitrogen monoxide (NO), 1,000 ppm i-C4 H10 , and an 8% O2 and N2 balance. The catalyst was carried out at temperatures between 250–450°C and a contact time of 20 minutes. It was found that NOx was effectively adsorbed in the presence of oxygen. The NOx storage capacity of K2 O/Al2 O3 was higher than that of BaO/Al2 O3. The NOx storage capacity for K2 O/Al2 O3 decreased with increasing temperature and achieved a maximum at 250°C. Potassium loading higher than 15% in the catalyst negatively affected the morphological properties. The combination of Ba and K loading in the catalyst led to an improvement in the catalytic activity compared to its single metal catalysts. As a conclusion, mixed metal oxide was a potential catalyst for de-NOx process in meeting the stringent diesel engine exhaust emissions regulations. The catalysts were characterized by a number of techniques and measurements, such as X-ray diffraction (XRD), electron affinity (EA), a scanning electron microscope (SEM), Brunner-Emmett-Teller (BET) to measure surface area, and pore volume and pore size distribution assessments.