scholarly journals Combination of LNT and SCR for NOx reduction in passenger car applications

2014 ◽  
Vol 157 (2) ◽  
pp. 60-67
Author(s):  
Teuvo MAUNULA

The removal of NOx and particulate emissions in light-duty diesel vehicles will require the use of aftertreatment methods like Diesel Particulate Filters (DPF) and Selective Catalytic Reduction (SCR) with urea and Lean NOx Trap (LNT) (Euro 6 and beyond). A new concept is the combination of LNT + SCR, which enables on-board synthesis of ammonia (NH3), which reacts with NOx on the SCR catalyst. The main application for this kind system will be lighter passenger cars, where LNTs may be used instead of full urea-SCR system. That particular combinatory system was investigated by developing platinum (Pt) and rhodium (Rh) containing LNTs and SCR catalysts in this study. In the use conditions, the maximum temperature may reach temperatures up to 800 °C and NOx reduction reactions should proceed without NO2 assistance in the SCR position after LNT and DPF. PtRh/LNT with the total loadings of 85 g/cft (2.8 g/L) and higher resulted in a high NOx efficiency above 80–90% with a broad operation window in the laboratory simulations. In the experimental conditions, a higher NH3 concentration after LNT was essential to simulate well the operation of SCR catalysts. The developed Cu-SCR catalyst showed a high hydrothermal durability up to the ageing temperature of 800 °C and a wide operation window without the NO2 assistance (NO only in feed). Fe-SCR and V-SCR catalysts were more dependent on NO2. A studied concept had an air injection after LNT to keep SCR condition always in lean side, where the SCR reaction was promoted by oxygen resulting in high reduction selectivity to nitrogen (N2) without NH3 emissions. The simulations in reaction conditions and system design resulted in the proposals for the optimal design and main reaction mechanism in DOC + DPF + LNT + SCR systems.

Author(s):  
Michael A. Smith ◽  
Christopher D. Depcik ◽  
Stefan Klinkert ◽  
John W. Hoard ◽  
Stanislav V. Bohac ◽  
...  

One approach for nitrogen oxides (NOx) emission control of medium duty diesel engines is through the use of a combination Lean NOx Trap and Selective Catalytic Reduction (LNT-SCR) catalyst system. In this system, part of the NOx conversion occurs via an NH3 SCR catalyst that is dependent on the NO2 to NOx ratio of the feed gas with NO2 being a more advantageous oxidizer. One benefit of using this system is the conversion of NO to NO2 over the LNT which increases the NO2:NOx ratio of the feed gas to the SCR catalyst. An experimental study has been performed to investigate the NO2-NH3 reaction for an Fe-based zeolite SCR catalyst using a bench top flow reactor. The increase in NO2 concentration at the inlet of the SCR results in the formation of large quantities of N2O from 200°C to 400°C. Further experiments determined that N2O and NH3 react above 350°C. This has led to a hypothesis that one primary SCR reaction (Slow SCR) can be replaced with two reaction steps featuring NH3, NO2, and N2O. As a result, this paper proposes five NOx reduction reactions as part of a global mechanism, which would account for the observed experimental behavior.


2021 ◽  
Author(s):  
Alejandro Calle-Asensio ◽  
Juan José Hernández ◽  
José Rodríguez-Fernández ◽  
Víctor Domínguez-Pérez

Abstract Advanced biofuels and electrofuels, among which are medium-long chain alcohols, have gained importance in the transport sector with the enforcement of the EU Renewable Energy Directive (2018/2001). In parallel, last European emission regulations have become much more restrictive regarding NOx, so vehicle manufacturers have been forced to incorporate lean NOx trap (LNT) and/or selective catalytic reduction (SCR). Thus, the combination of modern DeNOx devices and the upcoming higher contribution of sustainable biofuels is a new challenge. In this work, two Euro 6 diesel vehicles, one equipped with LNT and the other with ammonia-SCR, have been tested following the Worldwide harmonized Light-duty vehicles Test Cycle (WLTC) at warm (24°C) and cold (−7°C) conditions using conventional diesel fuel and a diesel-butanol (90/10% vol.) blend. While the effect of butanol on the LNT efficiency was not significant, its influence on the SCR performance was notable during the low and medium-speed phases of the driving cycle, mainly under warm climatic conditions. Despite of the lower NOx concentration at the catalyst inlet, the worst efficiency of the SCR with butanol could be attributed to hydrocarbons deposition on the catalyst surface, which inhibits the NOx reduction reactions with ammonia. Moreover, the LNT was not sensitive to the ambient temperature while the SCR performance greatly depended on this parameter.


Author(s):  
Amin Reihani ◽  
Brent Patterson ◽  
John Hoard ◽  
Galen B. Fisher ◽  
Joseph R. Theis ◽  
...  

Lean NOx Traps (LNTs) are often used to reduce NOx on smaller diesel passenger cars where urea-based Selective Catalytic Reduction (SCR) systems may be difficult to package. However, the performance of LNTs at temperatures above 400°C needs to be improved. The use of Rapidly Pulsed Reductants (RPR) is a process in which hydrocarbons are injected in rapid pulses ahead of the LNT in order to improve its performance at higher temperatures and space velocities. This approach was developed by Toyota and was originally called Di-Air (Diesel NOx aftertreatment by Adsorbed Intermediate Reductants) [1]. There is a vast parameter space that needs to be explored in order to maximize the NOx conversion at high temperatures and flow rates while minimizing the fuel penalty associated with the hydrocarbon injections. Four parameters were identified as important for RPR operation: (1) the flow field and reductant mixing uniformity; (2) the pulsing parameters including the pulse frequency, duty cycle, and rich magnitude; (3) the reductant type; and (4) the catalyst composition, including the type and loading of precious metal, the type and loading of NOx storage material, and the amount of oxygen storage capacity (OSC). In this study, RPR performance was assessed between 150°C and 650°C with several reductants including dodecane, propane, ethylene, propylene, H2, and CO. A novel injection and mixer system was designed that allowed for the investigation of previously unexplored areas of high frequency injections up to f = 100Hz. Under RPR conditions, H2, CO, dodecane, and C2H4 provided approximately 80% NOx conversion at 500°C, but at 600°C the conversions were significantly lower, ranging from 40 to 55%. The NOx conversion with C3H8 was low across the entire temperature range, with a maximum conversion of 25% near 300°C and essentially no conversion at 600°C. In contrast, C3H6 provided greater than 90% NOx conversion over a broad range of temperature between 280°C and 630°C. Among the hydrocarbons, this suggested that the high temperature NOx conversion with RPR improves as the reactivity of the hydrocarbon increases.


Catalysts ◽  
2020 ◽  
Vol 10 (5) ◽  
pp. 552
Author(s):  
Johanna Englund ◽  
Sandra Dahlin ◽  
Andreas Schaefer ◽  
Kunpeng Xie ◽  
Lennart Andersson ◽  
...  

We have investigated how the exhaust gases from a heavy-duty Euro VI engine, powered with biogas impact a vanadium-based selective catalytic reduction (SCR) catalyst in terms of performance. A full Euro VI emission control system was used and the accumulation of catalyst poisons from the combustion was investigated for the up-stream particulate filter as well as the SCR catalyst. The NOx reduction performance in terms of standard, fast and NO2-rich SCR was evaluated before and after exposure to exhaust from a biogas-powered engine for 900 h. The SCR catalyst retains a significant part of its activity towards NOx reduction after exposure to biogas exhaust, likely due to capture of catalyst poisons on the up-stream components where the deactivation of the oxidation catalyst is especially profound. At lower temperatures some deactivation of the first part of the SCR catalyst was observed which could be explained by a considerably higher surface V4+/V5+ ratio for this sample compared to the other samples. The higher value indicates that the reoxidation of V4+ to V5+ is partially hindered, blocking the redox cycle for parts of the active sites.


Catalysts ◽  
2019 ◽  
Vol 9 (11) ◽  
pp. 929 ◽  
Author(s):  
Auvray ◽  
Mihai ◽  
Lundberg ◽  
Olsson

Lean nitric oxide (NOx)-trap (LNT) and selective catalytic reduction (SCR) are efficient systems for the abatement of NOx. The combination of LNT and SCR catalysts improves overall NOx removal, but there is a risk that the SCR catalyst will be exposed to high temperatures and rich exhaust during the LNTs sulfur regeneration. Therefore, the effect of exposure to various rich conditions and temperatures on the subsequent SCR activity of a Cu-exchanged chabazite catalyst was studied. CO, H2, C3H6, and the combination of CO + H2 were used to simulate rich conditions. Aging was performed at 800 °C, 700 °C, and, in the case of CO, 600 °C, in a plug-flow reactor. Investigation of the nature of Cu sites was performed with NH3-temperature-programed desorption (TPD) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFT) of probe molecules (NH3 and NO). The combination of CO and H2 was especially detrimental to SCR activity and to NH3 oxidation. Rich aging with low reductant concentrations resulted in a significantly larger deactivation compared to lean conditions. Aging in CO at 800 °C caused SCR deactivation but promoted high-temperature NH3 oxidation. Rich conditions greatly enhanced the loss of Brønsted and Lewis acid sites at 800 °C, indicating dealumination and Cu migration. However, at 700 °C, mainly Brønsted sites disappeared during aging. DRIFT spectroscopy analysis revealed that CO aging modified the Cu2+/CuOH+ ratio in favor of the monovalent CuOH+ species, as opposed to lean aging. To summarize, we propose that the reason for the increased deactivation observed for mild rich conditions is the transformation of the Cu species from Z2Cu to ZCuOH, possibly in combination with the formation of Cu clusters.


2015 ◽  
Vol 4 (2) ◽  
pp. 263-269 ◽  
Author(s):  
M. Dietrich ◽  
D. Rauch ◽  
U. Simon ◽  
A. Porch ◽  
R. Moos

Abstract. To meet today's emission standards, the ammonia-based selective catalytic reduction (SCR) has become the major NOx control strategy for light and heavy diesel engines. Before NOx reduction can proceed, adsorption of ammonia on the acidic sites of the catalyst is necessary. For improvements in efficiency and control of the exhaust gas aftertreatment, a better understanding of the ammonia storage on the acidic sites of zeolite-based SCR catalysts is needed. Thereby, the correlation of dielectric properties of the catalyst material itself with the ammonia storage is a promising approach. Recently, a laboratory setup using microwave cavity perturbation to measure the dielectric properties of catalyst material has been described. This study shows the first experimental data on zeolite-based SCR materials in their H-form. The SCR powder samples are monitored by microwave cavity perturbation while storing and depleting ammonia, both with and without admixed NOx at different temperatures. Its complex dielectric permittivity is found to correlate closely with the stored mass of ammonia. The influence of the temperature and the Si / Al ratio of the zeolite to the ammonia storage behavior are also examined. These measurements disclose different temperature dependencies and differing sensitivities to ammonia storage for both real and imaginary parts of the complex permittivity. The apparent constant sensitivity of the real part can be related to the polarity of the adsorbed ammonia molecules, whereas the imaginary part depends on the Si / Al ratio and is related to the conductivity mechanisms of the zeolite material by proton hopping. It provides information about the zeolite structure and the number of (and the distance between) acidic storage sites, in addition to the stored ammonia mass.


Author(s):  
Vitaly Y. Prikhodko ◽  
Josh A. Pihl ◽  
Samuel A. Lewis ◽  
James E. Parks

Core samples cut from full size commercial Fe- and Cu-zeolite SCR catalysts were exposed to a slipstream of raw engine exhaust from a 1.9-liter 4-cylinder diesel engine operating in conventional and PCCI combustion modes. Subsequently, the NOx reduction performance of the exposed catalysts was evaluated on a laboratory bench-reactor fed with simulated exhaust. The Fe-zeolite NOx conversion efficiency was significantly degraded, especially at low temperatures (<250°C), after the catalyst was exposed to the engine exhaust. The degradation of the Fe-zeolite performance was similar for both combustion modes. The Cu-zeolite was much more resistant to HC fouling than the Fe-zeolite catalyst. In the case of the Cu-zeolite, PCCI exhaust had a more significant impact than the exhaust from conventional combustion on the NOx conversion efficiency. For all cases, the clean catalyst performance was recovered after heating to 600°C. GC-MS analysis of the HCs adsorbed to the catalyst surface provided insights into the observed NOx reduction performance trends.


2019 ◽  
Vol 9 (9) ◽  
pp. 2152-2162 ◽  
Author(s):  
Xavier Auvray ◽  
Ann Grant ◽  
Björn Lundberg ◽  
Louise Olsson

In the combined lean NOx trap (LNT) and selective catalytic reduction (SCR) concept, the SCR catalyst can be exposed to rich conditions during deSOx of the LNT.


Author(s):  
Yongbo Du ◽  
Chang’an Wang ◽  
Xiaoyang Wei ◽  
Qiang Lv ◽  
Yonggang Zhao ◽  
...  

The sodium content in Zhundong coal is extremely high, which can accelerate the deactivation of the V-W-TiO2 selective catalytic reduction (SCR) catalysts. Sulfuric acid solution (H2SO4) washing has been verified as a famous method to regenerate the de-NOx performance for catalyst which has been poisoned by alkali metals. However, the performance of the regenerated catalyst in practice still needs to be investigated. In the present study, the resistance to sulfur dioxide (SO2) and the mechanical strength of the regenerated catalyst were experimentally studied as well as the continuous operation performances under several conditions. The results indicate that the de-NOx activity of H2SO4 regenerated catalyst is chemically stable below 300 °C and thermally stable below 450 °C. However, the catalytic activity of the regenerated catalyst could suffer a decline during operating under the SCR atmosphere at 450 °C, which is different from the fresh catalyst. Besides, the regenerated catalyst shows good SO2 resistance, whereas the mechanical strength is likely to be affected by the H2SO4 washing treatment.


Catalysts ◽  
2020 ◽  
Vol 10 (2) ◽  
pp. 228
Author(s):  
Marina Cortés-Reyes ◽  
Concepción Herrera ◽  
María Ángeles Larrubia ◽  
Luis J. Alemany

The behavior and operation parameters were analyzed for the hybrid LNT-SCR (Lean NOx-Trap–Selective Catalytic Reduction) system with advanced catalyst formulations. Pt-Ba-K/Al2O3 was used as an NSR (NOx Storage and Reduction) or LNT catalyst effective in NOx and soot simultaneous removal whereas Cu-SAPO-34 with 2 wt.% of copper inside the structure was the small pore zeolite employed as the SCR catalyst. Under alternating and cyclic wet conditions, feeding volumetric concentrations of 1000 ppm of NO, 3% of O2, 1.5% of water, 0.3% of CO2, and H2 as a reductant, the NOx-conversion values were above 95% and a complete mineralization to nitrogen was registered using θ ≤ 3 (20 s of regeneration) and a hydrogen content between 10,000 and 2000 ppm in the whole temperature range tested. An excess of hydrogen fed (above 1% v/v) during the rich phase is unnecessary. In addition, in the low temperature range below 250 °C, the effect is more noticeable due to the further ammonia production and its possible slip. These results open the way to the scale up of the coupled catalytic technologies for its use in real conditions while controlling the influence of the operation map.


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