Influence of the type of reducing agent (H2, CO,C3H6 and C3H8) on the reduction of stored NO X in a Pt/BaO/Al2O3 model catalyst

In this investigation, a comparative study for a NO _X storage catalytic system was performed focusing on the parameters that affect the reduction by using different reductants (H₂, CO, C₃H₆ and C₃H₈) and different temperatures (350, 250 and 150 °C), for a Pt/BaO/Al₂O₃ catalyst. Transient experiments show that H₂ and CO are highly efficient reductants compared to C₃H₆ which is somewhat less efficient. H₂ shows a significant reduction effect at relatively low temperature (150 °C) but with a low storage capacity. We find that C₃H₈ does not show any NO _X reduction ability for NO _X stored in Pt/BaO/Al₂O₃ at any of the temperatures. The formation of ammonia and nitrous oxide is also discussed.

     

Sulfur deactivation and regeneration of Pt/BaO/Al2O3 and Pt/SrO/Al2O3 NO x storage catalysts

Transient experiments were performed to study sulfur deactivation and regeneration of Pt/BaO/Al₂O₃ and Pt/SrO/Al₂O₃ NO _x storage catalysts. It was found that the strontium-based catalysts are more easily regenerated than the barium-based catalysts and that a higher fraction of the NO _x storage sites are regenerated when H₂ is used in combination with CO₂ compared to H₂ only.     

Kinetic modeling of Fe‐BEA as NH3‐SCR catalyst—effect of phosphorous

The focus of this work is to investigate whether a previously developed microkinetic deactivation model for hydrothermally treated Fe‐BEA as NH₃‐SCR catalyst can be applied to describe chemical deactivation of Fe‐BEA due to phosphorous exposure. The model describes the experiments well for Fe‐BEA before and after phosphorous exposure by decreasing the site density, representing deactivation of sites due to formation of metaphosphates blocking the active iron sites, while the kinetic parameters are kept constant. Furthermore, the results show that the activity for low‐temperature selective catalytic reduction (SCR) is very sensitive to loss of active monomeric iron species due to phosphorous poisoning compared to high‐temperature SCR. Finally, the ammonia inhibition simulations show that exposure to phosphorous may affect the internal transport of ammonia between ammonia storage sites buffering the active iron sites, which results in a lower SCR performance during transient conditions. © 2014 American Institute of Chemical Engineers AIChE J, 61: 215–223, 2015     

Improved lean deNOx performance of Cu-ZSM-5 through alternative synthesis conditions for ZSM-5

A series of ZSM-5 samples with similar SiO₂/Al₂O₃ ratio was synthesised using different aluminum sources and by including varying amounts of calcium hydroxide during the synthesis. The samples were subsequently ion-exchanged with Cu-ions, and evaluated with respect to deNOx activity in the absence and presence of water. The choice of aluminum source and the presence of calcium hydroxide during the zeolite synthesis affected the lean deNOx activity of Cu-ZSM-5.     

Effect of Silver Loading on the Lean NOx Reduction with Methanol Over Ag–Al2O3

The influence of silver loading on the lean NO_x reduction activity using methanol as reductant has been studied for alumina supported silver catalysts. In general, increasing the silver loading (0–3 wt%), in Ag–Al₂O₃, shifts or extends the activity window, for lean NO_x reduction towards lower temperatures. In particular Ag–Al₂O₃ with 3 wt% silver is active for NO_x reduction under methanol-SCR conditions in a broad temperature interval (200–500 °C), with high activity in the low temperature range (maximum around 300 °C) typical for exhaust gases from diesel and other lean burn engines. Furthermore, increasing the C/N molar ratio enhances the reduction of NO_x. However, too high C/N ratios results in poor selectivity to N₂.     

Induced low temperature catalytic ignition by transient changes in the gas composition

The effect of gas composition changes on the low temperature activity for supported platinum model catalysts has been studied. By introducing well-controlled periodic O₂ pulses to a simple diluted gas mixture of CO and O₂, a substantial improvement of the low temperature oxidation activity was observed. The reason for low activity on noble metals at low temperatures is often attributed to self-poisoning by CO. The improved catalytic performance observed is proposed to origin from the transients causing a surface reactant composition that is favourable for the reaction rate, i.e. lower degree of self-poisoning. This was also confirmed by in situ Fourier transform infrared (FT-IR) spectroscopy in combination with mass spectrometry (MS) measurements, which gave evidence for the existence of a strong interplay between the gas phase concentration and the adsorbate composition for these catalysts.     

Influence of Synthesis Conditions for ZSM-5 on the Hydrothermal Stability of Cu-ZSM-5

The influence of syntheses parameters of zeolite ZSM-5 on the lean NO _x reduction activity and hydrothermal stability of Cu-ZSM-5 has been investigated. The hydrothermal stability of Cu-ZSM-5 was found to depend on the aluminium source used and on the presence of Ca(OH)₂ in the synthesis mixture for ZSM-5.     

Characterization of Particulate Matter from Direct Injected Gasoline Engines

The reactivity and reaction kinetics of particulate matter (PM) from direct injected gasoline (GDI) engines has been studied by O₂ and NO₂ based temperature programmed and isothermal step-response experiments, and the PM nano-structure has been characterized using HRTEM. The reactivity of the PM samples collected in filters during on-road driving was found to increase in the following order: Printex U < diesel < gasoline PI ≈ gasoline DI < ethanol for O₂ based combustion. The activation energies for O₂ and NO₂ based oxidation of PM collected from a GDI engine in an engine bench set-up was estimated to 146 and 71 kJ/mol respectively, which is comparable to corresponding values reported for diesel and model soot. Similar nano-structure features (crystallites plane dimensions, curvature and relative orientation) as observed for diesel soot were observed for gasoline PM.     

Influence of Ageing, Silver Loading and Type of Reducing Agent on the Lean NO x Reduction Over Ag–Al2O3 Catalysts

The influence of ageing temperature, silver loading and type of reducing agent on the lean NO _x reduction over silver–alumina catalysts was investigated with n-octane and bio-diesel (NExBTL) as reducing agent. The catalysts (2 and 6 wt% Ag–Al₂O₃) were prepared with a sol–gel method including freeze drying and the evaluation of NO _x reduction and aging were performed using a synthetic gas-flow reactor. The results indicate a relatively high NO _x reduction for both reducing agents. The hydrothermally treated 6 wt% Ag–Al₂O₃ sample displays a maximum NO _x reduction of 78 % at 350 °C for n-octane as reductant and the corresponding value for NExBTL is 60 %. Furthermore, the catalysts show high durability and an increase in activity for NO _x reduction after ageing at temperatures up to 650 °C, with n-octane as reducing agent.     

Characterization of a Pt-Pd combustion catalyst on an alumina washcoat,with and without prior hydrothermal treatment of the washcoat

Two Pt/Pd catalysts on cordierite monoliths were prepared by impregnating two differently treated alumina washcoats with 10 mol [Pt+Pd] per gram catalyst in the atomic ratio Pt/Pd=4.0. Both washcoats were first thermally treated, calcined, for 2 h at 550 °C in air and one of them was additionally treated, hydrothermally, in 100% steam for 2 h at 814 °C. The hydrothermally treated catalyst was more active for complete oxidation of xylene in air: its light-off temperature was 232 °C, compared to 259 °C for the sample calcined only. To explain this higher activity, both catalysts were characterized by BET surface area, pore-size distribution, hydrogen chemisorption, X-ray diffraction, TEM/STEM/EDS and low-energy ion scattering spectroscopy (LEIS). The catalyst with a hydrothermally treated washcoat had 30% lower surface area, larger alumina crystal size, higher degree of crystallization of alumina and larger average catalyst pore size (11 nm vs. 6 nm), than the one with the washcoat, treated only thermally. The LEIS results indicated a surface enrichment of Pd on both catalysts. The Pt signal in LEIS was higher for the hydrothermally treated sample.