A novel laboratory bench for practical evaluation of catalysts useful for simultaneous conversion of NOx and soot in diesel exhaust

This study deals with the development of a laboratory bench for the practical evaluation of catalysts that are useful for the direct conversion of NO_x and soot in the exhaust of diesel engines. The employed model exhaust is generated by using a diffusion burner with additionally dosing some gaseous components to the burner gas to obtain a realistic feed composition. The produced soot is extensively characterized by employing thermogravimetry, transmission electron microscopy, N₂ physisorption and temperature programmed techniques. The results of the different characterization methods show that the present soot is suitable for the intended catalytic investigations. The simultaneous conversion of NO_x and soot is examined like in practice, i.e. the soot is separated from the tail gas by a diesel particulate filter (DPF) that is coated with the catalyst. The deposited soot is then catalytically converted by NO_x and O₂ to form N₂ and CO₂. The conversions of NO_x and soot are measured by exclusively applying gas analysers, whereby a special experimental procedure is developed to determine the soot removal. Hence, additional soot related analytics are not required. To show the suitability of the constructed bench a Pt/Fe₂O₃/β-zeolite sample is taken as test catalyst that is reported to be very active in NO_x/soot reaction. The measurements performed with and without catalyst clearly show the effect of the used sample in simultaneous NO_x/soot conversion. We therefore consider the constructed laboratory bench to be a useful tool for testing and ranking catalytic materials.     

Reduction of NOx by H2 on WOx-Promoted Pt/Al2O3/SiO2 Catalysts Under O2-Rich Conditions

This work addresses the reduction of NO_x by H₂ under O₂-rich conditions using Al₂O₃/SiO₂-supported Pt catalysts with different loads of WO_x promotor. The samples were thoroughly characterised by N₂ physisorption, temperature-programmed desorption of CO, scanning electron microscopy, X-ray diffraction, laser raman spectroscopy, X-ray photoelectron spectroscopy and diffuse reflectance infrared fourier transform spectroscopy with probe molecule CO. The catalytic studies of the samples without WO_x showed pronounced NO_x conversion below 200 °C, whereas highest efficiency was related to small Pt particles. The introduction of WO_x provided increasing deNO_x activity as well as N₂ selectivity. This promoting effect was referred to an additional reaction path at the Pt-WO_x/Al₂O₃/SiO₂ interface, whereas an electronic activation of Pt by strong metal support interaction was excluded.

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Studies on the Effect of Physico‐Chemical Soot Properties and Feed Gas Composition on the Kinetics of Soot Oxidation on Fe2O3 Catalyst

Three commercial carbon black samples as well as self‐made C₃H₆ soot were investigated for their reactivity in the oxidation on an α‐Fe₂O₃ catalyst. These studies were performed by temperature programmed oxidation (TPO) using a packed bed. For reference purposes, TPO studies in the absence of the catalyst were made as well. The carbon black samples were characterized towards the content of C, H, N and O as well as higher heating value, specific surface area, moisture and volatile matter and were deemed to be suitable model substances for diesel soot of different maturity. The correlation of these physico‐chemical properties with the kinetics in catalytic TPO indicated that the soot oxidation on Fe₂O₃ is significantly affected by the initial number of surface oxygen compounds of the soot. The decomposition of these surface species causes the formation of active carbon sites, which are supposed to accelerate the soot oxidation.     

Simultaneous Catalytic Removal of Nitrogen Oxides and Soot from Diesel Exhaust Gas over Potassium Modified Iron Oxide

Iron oxide modified by potassium, i.e. Fe_1.9K_0.1O₃, exhibits high catalytic performance for the simultaneous conversion of soot and NO_x into CO₂ and N₂. The present study shows that long‐time treatment of the catalyst leads to a drastic decrease in the activity, whereas even the aged catalyst maintains considerable activity. On the other hand, long‐time treatment causes selective N₂ formation, i.e. no more formation of the byproduct N₂O. This alteration of catalytic performance is likely due to agglomeration of the promoter potassium being present at the surface of catalyst. Detailed experiments were carried out with a more realistic diesel model exhaust gas to confirm that Fe_1.9K_0.1O₃ is a suitable catalyst for the simultaneous removal of soot and NO_x between 350 and 480 °C. It was assumed that (CO) intermediates, formed by the catalytic reaction of NO_x and oxygen with the soot surface, are the reactive species in NO_x‐soot conversion.     

Effect of oxygen concentration on the NOx reduction with ammonia over V2O5–WO3/TiO2 catalyst

The catalytic reduction of NO_x in the typical operation temperatures and oxygen concentrations of diesel engines has been studied in the presence of V3W9Ti in a tubular flow reactor. The results have shown that the selective catalytic reduction is strongly affected by the oxygen concentration in low temperature range (150–275 °C). At higher temperatures, the reaction becomes independent of the O₂ concentration. The rate of the selective catalytic reduction of NO with ammonia may be considerably enhanced by converting part of the NO into NO₂. DRIFT measurements have shown that NH₃ and NO₂ are adsorbed on the catalyst surface on the contrary of NO. The experiments have shown that the decrease in N₂ selectivity of the SCR reaction is mainly due to the SCO of ammonia and to the formation of nitrous oxide.     

Study of the selective catalytic reduction of NOx on an efficient Fe/HBEA zeolite catalyst for heavy duty diesel engines

The present paper addresses the removal of NO_x from the exhaust of heavy duty vehicles using the SCR technique. The studies were conducted with a highly active H-BEA zeolite exhibiting a molar Si/Al ratio of 12.5 and a Fe load of 1.0 wt.% (1Fe/HBEA). The pronounced efficiency of 1Fe/HBEA is reflected by the apparent turnover frequency being superior to traditional V₂O₅/WO₃/TiO₂. The nature of the Fe sites was investigated with high resolution transmission electron microscopy (HRTEM), ⁵⁷Fe Mössbauer spectroscopy and powder X-ray diffraction (PXRD). In connection with previous examinations it is deduced that the iron sites represent octahedrally coordinated high spin Fe³⁺ cations. Furthermore, highly dispersed species, which are the most active sites, are supposed to be paramagnetic, while oligomeric and particulate structures indicate superparamagnetic behaviour.The practical evaluation of the 1Fe/HBEA catalyst was systematically carried out including laboratory studies of granulated powder and honeycomb samples as well as engine bench tests. For the latter studies a coated honeycomb prototype was employed showing very similar efficiency as referred to a commercial V₂O₅/WO₃/TiO₂ pattern.Furthermore, 1Fe/HBEA exhibits pronounced hydrothermal stability after aging at 550 °C which represents an elevated exhaust temperature of heavy duty vehicles. The aging caused no change in fast SCR, i.e. when a c(NO₂)/c(NO_x) ratio of 0.5 was used, and only minor decline in standard SCR. The slight aging effect is mainly referred to little decrease in BET surface area and NH₃ uptake, respectively. PXRD indicated maintenance of the BEA structure, whereas ²⁷Al nuclear magnetic resonance spectroscopy showed removal of some Al from the zeolite framework. Contrary, UV–vis spectroscopy evidenced no effect of hydrothermal aging on the composition of the Fe sites. Finally, the catalyst also maintained its efficiency after SO₂ aging at 300 °C. Diffuse reflectance infrared Fourier transform spectroscopic studies showed adsorption of molecular SO₂ on the zeolite substrate releasing already at about 400 °C.     

Study of the reaction of NOx and soot on Fe2O3 catalyst in excess of O2

This study addresses the catalytic reaction of NO_x and soot into N₂ and CO₂ under O₂-rich conditions. To elucidate the mechanism of the soot/NO_x/O₂ reaction and particularly the role of the catalyst -Fe₂O₃ is used as model sample. Furthermore, a series of examinations is also made with pure soot for reference purposes. Temperature programmed oxidation and transient experiments in which the soot/O₂ and soot/NO reaction are temporally separated show that the NO reduction occurs on the soot surface without direct participation of the Fe₂O₃ catalyst. The first reaction step is the formation of CC(O) groups that is mainly associated with the attack of oxygen on the soot surface. The decomposition of these complexes leads to active carbon sites on which NO is adsorbed. Furthermore, the oxidation of soot by oxygen provides a specific configuration of active carbon sites with suitable atomic orbital orientation that enables the chemisorption and dissociation of NO as well as the recombination of two adjacent N atoms to evolve N₂. Moreover, carbothermal reaction, high resolution transmission electron microscopy and isotopic studies result in a mechanistic model that describes the role of the Fe₂O₃ catalyst. This model includes the dissociative adsorption of O₂ on the iron oxide, surface migration of the oxygen to the contact points of soot and catalyst and then final transfer of O to the soot. Moreover, our experimental data suggest that the contact between both solids is maintained up to high conversion levels thus resulting in continuous oxygen transfer from catalyst to soot. As no coordinative interaction of soot and Fe₂O₃ catalyst is evidenced by diffuse reflectance infrared Fourier transform spectroscopy a van der Waals type interaction is supposed.     

The simultaneous reduction of nitric oxide and soot in emissions from diesel engines

Recent studies demonstrate that the decomposition of nitric oxide on a soot molecule forms surface nitrogen and oxygen. The surface nitrogen can be recombined to gaseous N₂ while the surface oxygen desorbs from the soot molecule as CO. This non-catalytic conversion of gaseous NO into N₂ is investigated using density functional theory, transition state theory and a kinetic Monte-Carlo (kMC) simulation. The results are validated against experiments. A mechanism for the conversion of NO to N₂ on a soot surface is explored. The geometries of the intermediate stable species as well as the transition states were optimized to identify the different reaction steps. The forward and backward reaction rate of each intermediate reaction is calculated applying transition state theory. A kMC simulation using the current rates and intermediate species demonstrates feasible mechanisms for the conversion of NO to N₂ on a soot surface. It is also suggested that a portion of NO is trapped on the soot surface and this increases during the reaction and blocks the active carbon sites inhibiting further reactions. By combining different theoretical techniques in a multi-scale model, we are able to describe the conversion of soot in the presence of NO accurately.     

CO2 Methanation on Fe Catalysts Using Different Structural Concepts

The hydrogenation of carbon dioxide towards methane and water is evaluated on different types of iron catalysts. The catalysts refer to different structural concepts implying a bare iron oxide, a silica-supported and a core-shell system. Highest CO₂ conversion of about 20 % is achieved with the bulk catalysts and the supported material. However, although revealing reduced CH₄ formation rate, the core-shell catalyst exhibits pronounced resistance against coke formation as well as thermal sintering and particle attrition upon syngas reaction.