Aleksey Yezerets

Overview of the Fundamental Reactions and Degradation Mechanisms of NOx Storage/Reduction Catalysts

Abstract Over the last several years, nitrogen oxide(s) (NOx) storage/reduction (NSR) catalysts, also referred to as NOx adsorbers or lean NOx traps, have been developed as an aftertreatment technology to reduce NOx emissions from lean‐burn power sources. NSR operation is cyclic: during the lean part of the cycle, NOx are trapped on the catalyst; intermittent rich excursions are used to reduce the NOx to N2 and restore the original catalyst surface; and lean operation then resumes. This review will describe the work carried out in characterizing, developing, and understanding this catalyst technology for application in mobile exhaust‐gas aftertreatment. The discussion will first encompass the reaction process fundamentals, which include five general steps involved in NOx reduction to N2 on NSR catalysts; NO oxidation, NO2 and NO sorption leading to nitrite and nitrate species, reductant evolution, NOx release, and finally NOx reduction to N2. Major unresolved issues and questions are listed at the end of each of the reaction process fundamental sections. Degradation mechanisms and their effects on NSR catalyst performance are also described in relation to these generalized reactions. Since at this stage it does not appear possible to arrive at a complete and consistent mechanistic model describing the broad, existing experimental phenomenology for these processes, this review is primarily focused on summarizing and evaluating literature data and reconciling the many differences presented.

Dynamic multinuclear sites formed by mobilized copper ions in NOx selective catalytic reduction

X-ray vision spies copper on the move Copper ions in zeolites help remove noxious nitrogen oxides from diesel exhaust by catalyzing their reaction with ammonia and oxygen. Paolucci et al. found that these copper ions may move about during the reaction (see the Perspective by Janssens and Vennestrom). Zeolite catalysts generally fix metals in place while the reacting partners flow in and out of their cagelike structures. In this case, though, x-ray absorption spectroscopy suggested that the ammonia was mobilizing the copper ions to pair up as they activated oxygen during the catalytic cycle. Science, this issue p. 898; see also p. 866 Copper ions can move about and pair up in a zeolite framework as they catalyze nitric oxide removal from diesel exhaust. Copper ions exchanged into zeolites are active for the selective catalytic reduction (SCR) of nitrogen oxides (NOx) with ammonia (NH3), but the low-temperature rate dependence on copper (Cu) volumetric density is inconsistent with reaction at single sites. We combine steady-state and transient kinetic measurements, x-ray absorption spectroscopy, and first-principles calculations to demonstrate that under reaction conditions, mobilized Cu ions can travel through zeolite windows and form transient ion pairs that participate in an oxygen (O2)–mediated CuI→CuII redox step integral to SCR. Electrostatic tethering to framework aluminum centers limits the volume that each ion can explore and thus its capacity to form an ion pair. The dynamic, reversible formation of multinuclear sites from mobilized single atoms represents a distinct phenomenon that falls outside the conventional boundaries of a heterogeneous or homogeneous catalyst.

Experimental determination of the kinetics of Diesel soot oxidation by O2: Modeling consequences

Several complementary experimental techniques were applied to investigate kinetics of diesel soot oxidation by O 2 in an attempt to provide accurate data for modeling of the Diesel Particulate Filters regeneration process. For two diesel soot samples with measurably different properties, it was shown that the complexity of their overall kinetic behavior was due to an initial period of rapidly changing reactivity. This initial high reactivity was understood not to be related to the SOF, and was quantitatively correlated to the extent of soot pre-oxidation. This initial reactivity can affect the averaged apparent kinetic parameters, for example resulting in the lower apparent activation energy values. After the initial soot pre-oxidation, which consumed ∼10-25% of carbon, the remaining soot was behaving very uniformly, producing linear Arrhenius plots in a remarkably broad range of temperatures (330-610°C) and integral conversions (up to 90%). The two samples of diesel soot were found to behave differently even after the SOF desorption and pre-oxidation, with the measurable difference in the light-off characteristics (-20-30°C) and activation energies (126′3 and 143′3 kJ/mol). Good mathematical description of the results was obtained using the hypothesis that reaction order with respect to soot mass is close to unity. Implications of the first order are discussed, including its effect on the model structure.

Deactivation of Cu-SSZ-13 by SO2 exposure under SCR conditions

A deactivation study of Cu-SSZ-13 has been conducted using SO2 exposure under SCR conditions and examining its effect on different reactions involving NH3-SCR. Several reactions, including NH3 storage/TPD, NO/NH3 oxidation, standard SCR, fast SCR and SCR with 75% NO2, as well as NH3–NO2 storage/TPD, were investigated at a temperature range of 100–400 °C after exposing the catalyst to 30 ppm SO2 under SCR conditions at 300 °C for 90 min. The catalyst was characterized using XRD, BET, ICP-SFMS and H2-TPR. The BET surface area and pore volume decreased after the sulfur treatment presumably due to blocking by sulfur and/or ammonium–sulfur species. It was found that sulfur was not uniformly deposited along the monolith channel. The deposition occurred from the inlet towards the outlet, as evident from ICP-SFMS measurements. Part of the sulfur was removed after an SCR experiment up to 400 °C. However, this removal was observed only in the inlet half of the sample and not in the outlet. Ammonia TPD experiments revealed that the sulfur poisoning resulted in additional sites that were capable of adsorbing ammonia, resulting in increased ammonia storage. Moreover, standard SCR was significantly deactivated by SO2 poisoning under SCR conditions. Due to the site-blocking effect of the ammonium–sulfur species, fewer copper sites are likely available for the redox SCR cycle. Furthermore, the effect of sulfur poisoning on NH3 oxidation and NO2-SCR as well as N2O production in various SCR reactions were observed. Finally, it was found that the conditions for the sulfur poisoning were critical in which SO2 deactivation under SCR conditions (NH3 + NO + O2 + H2O) was more severe compared to SO2 poisoning in O2 + H2O alone.

The Effect of NO2/NOx Feed Ratio on the NH3-SCR System Over Cu–Zeolites with Varying Copper Loading

In this study we examine the NO/NO2–NH3-SCR system over Cu–BEA with varying Cu loading. Significantly higher selective catalytic reduction (SCR) activity is observed at low temperature on highly loaded copper samples, whereas the reverse trend is noticed at high temperature. The N2O formation is substantially increased over “over-exchanged” Cu sites, where Cu co-ordinate to one Al and charge-balanced with one OH-group. This is also the case for NO2 reaction with NH3 to produce NO. Using transient experiments the formation/decomposition of ammonium nitrate species are examined. The decomposition depends on the temperature, the sequence of the feed as well as the type of copper species present.Graphical Abstract

Bifunctional nature of SnO2/γ-Al2O3 catalysts in the selective reduction of NOx

Abstract In lean NO x reduction by C 3 H 6 over SnO 2 /Al 2 O 3 , both SnO 2 and Al 2 O 3 participate in the reaction. C 3 H 6 is activated on SnO 2 active sites to form oxygenated intermediates such as acrolein and acetaldehyde. The oxygenates subsequently react with NO x on Al 2 O 3 to yield N 2 .

Structural and kinetic changes to small-pore Cu-zeolites after hydrothermal aging treatments and selective catalytic reduction of NOx with ammonia

Three small-pore, eight-membered ring (8-MR) zeolites of different cage-based topology (CHA, AEI, RTH), in their proton- and copper-exchanged forms, were first exposed to high temperature hydrothermal aging treatments (1073 K, 16 h, 10% (v/v) H2O) and then to reaction conditions for low temperature (473 K) standard selective catalytic reduction (SCR) of NOx with ammonia, in order to study the effect of zeolite topology on the structural and kinetic changes that occur to Cu-zeolites used in NOx abatement. UV-visible spectra were collected to monitor changes to Cu structure and showed that band intensities for isolated, hydrated Cu2+ cations (∼12 500 cm−1) remain constant after hydrothermal aging, but decrease in intensity upon subsequent exposure to low temperature SCR reaction conditions. Standard SCR rates (per Cu, 473 K), activation energies, and reaction orders are similar between Cu-AEI and Cu-CHA zeolites before and after hydrothermal aging, although rates are lower after hydrothermal aging as expected from the decreases in intensity of UV-visible bands for Cu2+ active sites. For Cu-RTH, rates are lower (by 2–3×) and apparent activation energies are lower (by ∼2×) than for Cu-AEI or Cu-CHA. These findings suggest that the RTH framework imposes internal transport restrictions, effectively functioning as a one-dimensional framework during SCR catalysis. Hydrothermal aging of Cu-RTH results in complete deactivation and undetectable SCR rates, despite X-ray diffraction patterns and Ar micropore volumes (87 K) that remain unchanged after hydrothermal aging treatments and subsequent SCR exposure. These findings highlight some of the differences in low temperature SCR behavior among small-pore Cu-zeolites of different topology, and the beneficial properties conferred by double six-membered ring (D6R) composite building units. They demonstrate that deleterious structural changes to Cu sites occur after exposure to hydrothermal aging conditions and SCR reactants at low temperatures, likely reflecting the formation of inactive copper-aluminate domains. Therefore, the viability of Cu-zeolites for practical low temperature NOx SCR catalysis cannot be inferred solely from assessments of framework structural integrity after hydrothermal aging treatments, but also require Cu active site and kinetic characterization after hydrothermally aged zeolites are exposed to low temperature SCR reaction conditions.

Final Report of a CRADA Between Pacific Northwest National Laboratory and Cummins, Incorporated (CRADA No.PNNL/283): “Enhanced High and Low Temperature Performance of NOx Reduction Catalyst Materials”

In this annual CRADA program report, we will briefly highlight results from our recent studies of the stability of candidate K-based high temperature NSR materials, and comparative studies of low temperature performance of SSZ-13 and SAPO-34 CHA catalysts; in particular, recent results comparing Fe- and Cu-based CHA materials.

CRADA Final Report: Mechanisms of Sulfur Poisoning of NOx Adsorber Materials

This annual report will review progress of the initial 4 months of a three-year effort between Cummins Engine Company and Pacific Northwest National Laboratory to understand and improve the performance and sulfur tolerance of the materials used in the NOx adsorber after-treatment technology in order to meet both performance and reliability standards required for diesel engines. The goal of this project is to enable NOx after-treatment technologies that will meet both EPA 2007 emission standards and customer cost, reliability and durability requirements. The project will consist of three phases. First, the efforts will focus on understanding the current limitation of capture, regeneration and durability of existing NOx adsorber materials, especially with respect to their sulfur tolerance. With this developing understanding, efforts will also be focused on the optimization of the NOx absorber chemical and material properties to increase performance and durability over many regeneration cycles. We anticipate that improved materials will be tested and evaluated, in partnership with Cummins, on diesel vehicle engines over expected operating conditions.