NOx Reduction Research Articles

Numerical Investigation of CO and NO Production From Premixed Hydrogen/Methane Fuel Blends

Abstract There is significant interest in utilizing hydrogen as an energy carrier in a net-zero carbon energy economy. A variety of fundamental and practical issues associated with premixed hydrogen/methane combustion must be addressed, particularly flame flashback, combustion instabilities, and NOx emissions. Significantly less attention has been given to CO emissions from hydrogen blending. However, recent H2 blending engine tests have clearly noted major reductions in CO emissions, reductions which substantially exceed what would be expected based upon C atom mass balances in the fuel. Moreover, NOx, CO, and combustor operability always tradeoff with each other, and so, for example, these CO reductions can also enable operational or design modifications to reduce NOx emissions and/or wider operability windows. This paper addresses H2 blending effects on CO emissions, addressing both the direct influences on CO emissions, as well as how it influences NOx–CO tradeoffs. The paper presents computations that differentiate between the kinetic and equilibrium effects of H2 blending, as well as how H2 blending can lead to reductions in both NOx and CO by moving the Pareto front downward. Finally, this work suggests that H2 blending, in addition to its CO2 reductions, can also increase plant operational flexibility and so provide additional value propositions to an evolving electricity market.

Effect of modified Fe2O3/activated carbon catalysts for low-temperature CO selective catalytic reduction of NOx in underground diesel vehicle exhaust

The elimination of CO and NOx has practical significance for the control of exhaust pollutants from underground diesel vehicles. Catalytic reduction of NO by CO (CO-SCR) using activated carbon (AC) catalysts is considered a cost-effective and environmentally friendly denitrification method. In this study, Fe2O3/AC-based catalysts were prepared using an impregnation method and modified with different metals to investigate their impact on catalyst performance. The results demonstrated that the catalyst exhibited the highest denitrification efficiency when loaded with 10% Fe. The Mn-doped 10Fe/AC catalyst exhibited the best catalytic performance, with the highest NO conversion of 97.5% and CO removal rate of 83.3% at 240 °C. The effects of loading Mn, Ce, and La on the physical and chemical properties of the catalysts were analyzed using various characterization tools, and the reaction mechanism of the catalysts was investigated by in situ DRIFTS technique. The findings revealed that the strong synergistic interaction occurring between Mn and Fe led to an increase in the surface-adsorbed oxygen (Oα) and Fe3+, which produced more oxygen vacancies on the catalyst, thus improving the redox properties. The in-situ DRIFT results indicated that the addition of Mn enhanced the adsorption capacity of active NO and CO. For the CO-SCR reaction on Fe-Mn/AC catalyst, the E-R mechanism was followed at low temperature and the L-H mechanism was followed at high temperature.

Recent Advancements in Fe-Based Catalysts for the Efficient Reduction of NOx by CO.

The technology of CO selective catalytic reduction of NOx (CO-SCR) showcases the potential to simultaneously eliminate CO and NOx from industrial flue gas and automobile exhaust, making it a promising denitrification method. The development of cost-effective catalysts is crucial for the widespread implementation of this technology. Transition metal catalysts are more economically viable than noble metal catalysts. Among these, Fe emerges as a prominent choice due to its abundant availability and cost-effectiveness, exhibiting excellent catalytic performance at moderate reaction temperatures. However, a significant challenge lies in achieving high catalytic activity at low temperatures, particularly in the presence of O2, SO2, and H2O, which are prevalent in specific industrial flue gas streams. This review examines the use of Fe-based catalysts in the CO-SCR reaction and elucidates their catalytic mechanism. Furthermore, it also discusses various strategies devised to enhance low-temperature conversion, taking into account factors such as crystal phase, valence states, and oxygen vacancies. Subsequently, the review outlines the challenges encountered by Fe-based catalysts and offers recommendations to improve their catalytic efficiency for use in low-temperature and oxygen-rich environments.

The Catalytic Mechanisms and Design Strategies of Noble Metal Catalysts for Selective Reduction of NOx with CO

AbstractThe selective catalytic reduction of NOx by CO (CO‐SCR) is a viable method for simultaneously mitigating NOx and CO emissions in motor vehicle exhaust and industrial flue gases. Extensive research has been conducted on noble metal catalysts because of their superior catalytic activity and stability compared to non‐noble metals. Noble metal catalysts demonstrate efficient NOx conversion and high selectivity for N2. However, achieving high conversion, selectivity, and stability over a wide temperature range in the presence of excess O2, H2O, and SO2 remains a significant challenge. This review summarizes recent advancements in CO‐SCR over noble metal catalysts, providing insights for the development of CO‐SCR catalysts. This paper first examines the reaction mechanisms of CO‐SCR, followed by a discussion on the design and optimization strategies of noble metal catalysts, with a focus on composition and structural effects. This includes creating active metal sites, selecting appropriate supports, integrating catalytic additives, choosing monometallic nanoparticles, alloying, and using single‐atom catalysts. Finally, remaining challenges and potential avenues for future research have been suggested. The discovery of negatively charged noble metal single‐atom‐site catalysts presents new research opportunities.

Understanding the roles of Brønsted/Lewis acid sites on manganese oxide-zeolite hybrid catalysts for low-temperature NH3-SCR

Although metal oxide-zeolite hybrid materials have long been known to achieve enhanced catalytic activity and selectivity in NOx removal reactions through the inter-particle diffusion of intermediate species, their subsequent reaction mechanism on acid sites is still unclear and requires investigation. In this study, the distribution of Brønsted/Lewis acid sites in the hybrid materials was precisely adjusted by introducing potassium ions, which not only selectively bind to Brønsted acid sites but also potentially affect the formation and diffusion of activated NO species. Systematic in situ diffuse reflectance infrared Fourier transform spectroscopy analyses coupled with selective catalytic reduction of NOx with NH3 (NH3-SCR) reaction demonstrate that the Lewis acid sites over MnOx are more active for NO reduction but have lower selectivity to N2 than Brønsted acids sites. Brønsted acid sites primarily produce N2, whereas Lewis acid sites primarily produce N2O, contributing to unfavorable N2 selectivity. The Brønsted acid sites present in Y zeolite, which are stronger than those on MnOx, accelerate the NH3-SCR reaction in which the nitrite/nitrate species diffused from the MnOx particles rapidly convert into the N2. Therefore, it is important to design the catalyst so that the activated NO species formed in MnOx diffuse to and are selectively decomposed on the Brønsted acid sites of H-Y zeolite rather than that of MnOx particle. For the physically mixed H-MnOx+H-Y sample, the abundant Brønsted/Lewis acid sites in H-MnOx give rise to significant consumption of activated NO species before their inter-particle diffusion, thereby hindering the enhancement of the synergistic effects. Furthermore, we found that the intercalated K+ in K-MnOx has an unexpected favorable role in the NO reduction rate, probably owing to faster diffusion of the activated NO species on K-MnOx than H-MnOx. This study will help to design promising metal oxide-zeolite hybrid catalysts by identifying the role of the acid sites in two different constituents.

The enhanced SO2 resistance of Fe-Ti catalyst by W/SO42− co-modification for NH3-SCR: A combined experimental and DFT study

It remains a great challenge to improve the low-temperature SO2 resistance of catalysts applied for selective catalytic reduction of NOx with NH3 (NH3-SCR). This work develops an outstanding SO2-tolerant Fe-Ti (FT) catalyst by W/SO42− co-modification via a sol–gel method using Fe(NO3)3·9H2O, tetrabutyl titanate, ammonium tungstate and thiourea as raw materials. The physicochemical characterizations, in-situ diffuse reflectance infrared Fourier transform (DRIFT) measurements and density functional theory (DFT) calculations were combined to reveal the underlying mechanisms. Although W doping can effectively enhance the surface acidity, NH3 adsorption on Lewis acid sites can still be restrained by competitive adsorption of SO2, whereas SO42− modification can enhance the adsorption stability of NH3 without being affected by SO2. Simultaneously, the NO adsorption ability on Fe sites can be significantly enhanced by W/SO42− co-modification. Furthermore, the W doping or SO42− modification can induce conversion of Fe3+ to Fe2+ to affect the redox property of Fe species. A proper amount of Fe2+ suppressed the oxidizability of FT catalyst to inhibit NH3 overoxidation to enhance N2 selectivity, and created more oxygen vacancies to generate larger amount of chemisorbed oxygen to facilitate NH3 dehydrogenation and NO oxidation. More importantly, the inhibition effect of SO2 adsorption on Fe sites was strengthened by W/SO42− co-modification. Consequently, the W/SO42− co-modified FT catalyst exhibited high activity with >90 % of NO conversion and >95 % of N2 selectivity within a broad window of 275–450 °C and possessed superior SO2 + H2O tolerance at 275 °C.

NOx reduction scenarios under real-world driving conditions for light-duty diesel vehicles

This study analyze analyzes the impact of stringent emissions regulations on future NOx reductions. Using scenario analysis, NOx emissions of diesel light-duty vehicles from 2019 to 2040 are estimated using emission factors from real driving emissions data. The baseline scenario assumes current regulations will be maintained, while other scenarios assess the impact of implementing specific Euro standards as final regulations. If Euro 5 regulations are implemented by 2040, cumulative emissions will increase by 229.1 % compared to the baseline scenario. Implementing Euro 6 a/b/c regulations will increase by 156.2 %, while Euro 6 d-temp and Euro 6 d regulations will increase by 8.4 % and 0.7 %, respectively. These findings highlight the significant contribution of real driving emission test introduced with Euro 6 d-temp to NOx reduction. Furthermore, they indicate that Euro 6 d regulation has already achieved emission levels similar to those of the upcoming Euro 7 regulation.

Design of Hydrogen Combustion Engine (Conceptual Brainstorming)

Hydrogen combustion engines present a promising pathway for cleaner transportation, leveraging existing internal combustion engine (ICE) technologies. The design of hydrogen-fueled ICEs requires significant modifications to conventional gasoline or diesel engines due to hydrogen’s distinct combustion properties. This research outlines the key design considerations for hydrogen combustion engines, including fuel storage and injection, combustion chamber modifications, ignition control, and exhaust treatment. The study also discusses recent advancements in engine efficiency, NOx reduction, and dual-fuel systems, along with the challenges of implementing hydrogen-based ICEs in commercial applications. Keywords: hydrogen, combustion, design, ICE, alternative fuels

Electrocatalytic Synthesis of Organonitrogen Compounds via C−N Coupling from NOx and Carbon Source

AbstractNitrogen oxide (NOx) is an attractive nitrogen source. Electrocatalytic NOx reduction coupled with the conversion of carbon source molecules offers a potential route for sustainable synthesis of valuable nitrogenous organics. This review discusses recent progress on the synthesis of electrocatalytic organonitrogen compounds (such as oximes, amino acids, amines, amides and urea) via C−N coupling from NOx and carbon source. The electrocatalytic performance, catalyst structure and especially reaction mechanism are discussed. Current challenges, catalyst design principles, the understanding on reaction mechanisms, as well as possible strategies for improving reaction selectivity and activity are proposed, which will guide future researches in the electrocatalytic conversion of NOx and carbon source.

Effect of SBA-15 Morphology in the Catalytic Performance of Pt/Ce-SBA-15 Catalyst for NOx Reduction

Effect of SBA-15 Morphology in the Catalytic Performance of Pt/Ce-SBA-15 Catalyst for NOx Reduction

Analysis of Ozone Pollution and Precursor Control Strategies in the Pearl River Delta During Summer and Autumn Transition Season

To analyze the causes of ozone pollution in the Pearl River Delta （PRD） Region during the summer and autumn transition seasons, a case study was carried out in Guangzhou, which is located in the center of the PRD Region, to analyze the ozone photochemical production and destruction pathways as well as emission reduction scenarios using a box model based on comprehensive observation. The results showed that the stagnant meteorological conditions and high temperature during the observation period were suitable for the photochemical production of ozone, which led to widespread and prolonged ozone pollution. Aromatic hydrocarbons （AHs） contributed the most to the ozone formation potential （OFP）, and m/p-xylene, toluene, and o-xylene were the major three VOC species contributing to the OFP. Box model analysis revealed that the averaged net O3 production rate during the polluted period was 23.2×10-9 h-1 and the peak reached 39.2×10-9 h-1. The HO2·+NO and NO2+·OH reaction pathways contributed the most to the local photochemical ozone production （51.2%） and destruction （47.0%）, respectively. Observed ozone concentration was primarily controlled by both the local photochemical O3 production and the export-dominated transport. The RIR and EKMA analyses showed that O3 formation in Guangzhou during the summer-autumn transition seasons was mainly a VOC-limited regime and AHs showed the greatest sensitivity to O3 production. Toluene, m/p-xylene, o-xylene, n-butane, and propylene were the five key components affecting O3 generation. The analysis of reduction scenarios showed that reducing anthropogenic VOC emissions was the most favorable way to reduce O3 concentrations； however, if NOx emission was controlled after reducing VOCs, the O3 concentration would rebound in a short time. Our results suggested that the synergistic reduction of VOCs and NOx while mainly focusing on VOCs alleviation should be implemented to continuously reduce ozone concentrations in the future.

Liquid Nitrogen Exfoliation and Nanodispersion of WS2 for Thermocatalysts.

The efficient and clean exfoliation of single and/or few-layer nanosheets of WS2, a two-dimensional transition metal dichalcogenides, remains a significant challenge. In this study, a simple exfoliation method was proposed to produce ultrathin WS2 nanosheets by combining the liquid nitrogen exfoliation and nanodispersion techniques. This approach efficiently exfoliated WS2 into several layers of nanosheets via rapid temperature changes and mechanical stress without inducing defects or contamination. After five cycles of heating/liquid nitrogen and nanodispersion, the resulting WS2 nanosheets (WS2-5N ND) were confirmed to have been successfully exfoliated into 1-4 layers. When applied as a promoter in a thermocatalyst for the selective catalytic reduction of NOX using NH3, 2V3WS2/Ti (WS2-5N ND) exhibited excellent NOX conversion and N2 selectivity, along with excellent durability even in the presence of SO2. This result was greater than 2V3WS2/Ti (WS2-5N) subjected to only liquid nitrogen exfoliation, proving the importance of the simultaneous action of both methods. This method is expected to be an important contribution to ongoing research on high-performance WS2-based catalysts, thereby opening up potential opportunities for a wide range of applications.

Application End Evaluation of Electrostatic Precipitation for Control PM and NOx Emissions from Small-Scale Combustions

Electrostatic precipitators (ESPs) have shown promise in reducing particulate matter (PM) emissions, but their potential for simultaneous NOx reduction in small-scale combustion systems remains underexplored. This study focuses on using non-thermal plasma generated in a corona discharge to reduce PM and NOx emissions from small-scale combustion. ESP was specifically designed for a commercially available 15 kW boiler with wood pellet combustion and used with both positive and negative discharge polarity to control emissions without any chemical additives. ESP performance was evaluated across a range of specific input energies (SIE) in terms of particle mass and number concentrations and NOx concentrations obtained by continuous gas analysis. ESP ensured the reduction in PM concentrations from 48 mg/m3 to the magnitude of PM content in the ambient air. The highest precipitation efficiency was observed for particles in the 20–200 nm range. Concurrently, NOx emissions were reduced by up to 78%, from 178 mg/m3 to 39 mg/m3. These results were achieved at specific input energies of 36 for positive and 48 J/L for negative corona, which is significantly lower than those reported for many existing separate PM and NOx control systems. This study demonstrates the potential of ESPs as a compact, energy-efficient solution for simultaneous PM and NOx removal in small-scale combustion systems, offering promising implications for improving air pollution control technologies for small-scale combustion systems.

A novel approach of in-cylinder NOx control by inner selective non-catalytic reduction effect for high-pressure direct-injection ammonia engine

As an efficient hydrogen carrier and carbon-free fuel, ammonia shows great promise in realizing zero-carbon propulsions. However, challenges such as poor ignition stability, low combustion efficiency, and fuel-NOx emissions are yet to overcome. In this paper, the high-pressure direct-injection ammonia/diesel dual-fuel combustion mode (HPDF) with post injection strategy is proposed as a solution. The study reveals that HPDF combustion mode enables in-cylinder reduction of NOx, which is attributed to the selective non-catalytic reduction (SNCR) reaction. The results uncover that NH2, NH, and N radicals have a significant reducing effect on NO and NO2, while N2O serves as an important byproduct of the reduction reactions. Subsequently, the generated N2O can be further reduced to N2 through the involvement of O, H, and OH radicals. Building upon these findings, an innovative ammonia post injection method for reducing NOx emissions is explored. The post injection strategy effectively reduces the NOx emissions with only a minor decrease in indicated thermal efficiency, but an over-delayed post injection could also cause significant increase in N2O and unburned NH3 emissions. A post injection proportion of 20%-30% with appropriate post injection timing is found to achieve desired emission reduction. Overall, the HPDF combustion mode is a promising solution for ammonia engine, due to the high thermal efficiency and low nitrogen oxide emissions, as well as the ability to further reduce the NOx emissions through ammonia post injection strategy.

Ammonium Chloride Powder Feeding for the Simultaneous Reduction of NOx and Oxidation of Hg0 in the SCR Process

Ammonium Chloride Powder Feeding for the Simultaneous Reduction of NOx and Oxidation of Hg⁰ in the SCR Process

Low-Temperature Reduction of NOx by NH3 with Unity Conversion on Nanofilament MnO2/Activated Semi-Coke Catalyst.

Selective catalytic reduction of nitrogen oxides with NH3 at low temperatures remains a crucial goal for industrial applications. However, effective catalysts operating at 70-90 °C are rarely reported, limiting SCR scenarios to high-temperature conditions. Herein, we report a unique MnO2 nanofilament catalyst grown on activated semi-coke synthesized via a one-step in situ hydrothermal approach, which exhibits a stable and marked 100 % conversion rate of NO to N2 with 100 % selectivity at 90 °C, superior to the other prepared structures (nanowires, nanorods, and nanotubes). Temperature-programmed desorption shows a large number of acid sites on MnO2(NFs)/ASC, benefiting the formation of NH4 + ions. Meanwhile, diffuse reflectance infrared Fourier transform spectroscopy reveals the activation of NO with O2 to form bidentate nitrate/bridging nitrate NO2 intermediates via bidentate nitrate species, triggering the Fast SCR with NH3 at low temperatures. Such an effective, easy-to-prepare, and low-cost catalyst paves a new pathway for low-temperature SCR for a wide range of application scenarios.

Self-protected Chlorella@Mn catalyst with excellent resistance to alkali/alkaline earth metal for NOx reduction by NH3

In the selective catalytic reduction of NOx by NH3 (NH3-SCR), conventional Mn-based denitration catalysts often suffered from susceptibility to poisoning by alkali and alkaline earth metals, this paper presented an innovative self-protected Chlorella@Mn denitration catalyst. Remarkably, in the presence of high concentrations (2 wt%) of alkali and alkaline earth metal oxides, the Chlorella@Mn catalyst sustained a NOx conversion exceeding 96 % at 175 °C. At an even higher concentration (4 wt%), NOx conversion above 90 % at 175 °C, surface analysis revealed that POMn sites acted as sacrificial sites, binding to the alkali and alkaline earth metals, the Chlorella@Mn catalyst surface naturally carried a spectrum of acidic species (such as SO42−, PO3−, SiO32−), proficient in capturing alkali/alkaline earth metal effectively, elements such as S, P, and Si formed bonds with K, Na, Ca, and Mg. The synergistic protection of the active sites and the surface elements avoided the deactivation of the catalyst. The detrimental effects of high concentrations of alkali and alkaline earth metals were primarily due to promoting an excessively high valence state of Mn on the catalyst surface and the reduction or loss of NH3 adsorption and activation at Brønsted acid sites. This research provided valuable insights for advancing the development of low-temperature denitration catalysts with improved resistance to alkali and alkaline earth metal poisoning.

Ground ozone rise during the 2022 shanghai lockdown caused by the unfavorable emission reduction ratio of nitrogen oxides and volatile organic compounds

Ground-level ozone (O3) pollution has shifted from a scientific issue to a key focus of governmental action in China. In recent years, the concentration of NO2 in Shanghai has shown a decreasing trend of 3.7% annually, but ozone concentrations have exhibited significant interannual variability, particularly with a noticeable increase in 2022. This study focuses on investigating the mechanisms behind the increase in ozone concentration during the COVID-19 pandemic control period in 2022 in Shanghai, utilizing a combination of ground observation data, observation-based models, and chemical transport models for analysis. The results indicate that during the lockdown period, the mean values of daily maximum 8-h average O3 concentrations (MDA8 O3) in Shanghai increased by 17 μg/m³, with emission-related factors contributing 65.3%, primarily due to a blanket reduction in VOCs and NOx emissions during the lockdown, with a reduction ratio close to 1:1. However, this reduction ratio and intensity are not sufficiently reasonable to alleviate ozone pollution. Meanwhile, adverse meteorological conditions further exacerbated this effect, contributing 34.7%, with temperature rise having the greatest impact. Results from the chemical transport model show that with the total reduction in NOx and VOCs emissions unchanged, the greater the reduction in VOC emissions and the better the reduction effect on ozone pollution, reducing MDA8 O3 by approximately 10 μg/m³, especially for the control of reactive compounds such as alkenes, aromatics, and OVOCs. However, if the reduction ratio of NOx is greater than that of VOCs, ozone concentrations may not decrease but instead increase. This indicates that ozone concentration is influenced not only by the intensity of emissions reduction but also by the ratio of emissions reduction between NOx and VOCs. Our study emphasizes the critical role of carefully designed strategies, focusing on controlling the ratio of VOCs to NOx and increasing the intensity of VOCs reduction, to effectively alleviate ozone pollution in urban areas.

Numerical and Optimization Studies on Reactivity Controlled Compression Ignition Engine with Hydrogen and Split Injections

Abstract Effective abatement of harmful tail-pipe emissions from fossil fuel run engines is achieved through low-temperature combustion strategies; Reactivity Controlled Compression Ignition mode of operation has been successful among such concepts. The present work deals with numerical work performed using ANSYS Forte software with n-heptane as a high-reactivity fuel and hydrogen in different proportions as a low-reactivity fuel, respectively. With total energy fixed, the amount of hydrogen is varied from 0-80% fuel injection is regulated accordingly. Pertinent engine in-cylinder parameters with patterns are extracted, emphasizing the combustion phenomena of RCCI operation with the lowest possible emissions targeted, with the combined effects of hydrogen induction, Start of Injection, and split injections. The contours of fuel vapour and emission parameters are obtained to relate the performance with emissions. It is noted that with a split injection strategy at 50/50 and 75/25 split strategy and 45-50% energy share from hydrogen, the NOx, Soot reductions and thermal efficiency penalty are in the range of about 5.5%, 24% and 7.5%, respectively, also, with 30% EGR, about 95% NOx reduction but with higher soot values. A 75/25 split and advanced injection timing of 25obTDC resulted in the RCCI mode of operation with reduced soot emissions, and the use of EGR has resulted in high levels of soot and poor fuel efficiency. Among the models of machine learning tested, Random Forest regressor emerged as the most suitable, with higher R2 values, indicating better predictive capability.

Polymetallic MnW/Co3O4 porous composites derived from polyoxometalate-induced “cage-within-cage” zeolitic imidazolate frameworks with high efficiency towards NOx reduction

Exploitation of highly active, economical and environmentally friendly catalysts is the primary imperative for addressing the pivotal concerns confronting NOx pollution. Transition metal oxides have shown good application prospects in NOx purification due to their plentiful availability and affordable pricing. Herein, a confinement-pyrolysis strategy for preparation of MnW/Co3O4 composites with porous structures and high dispersion of active components transformed from polyoxometalate (POM)-encapsulated zeolitic imidazolate frameworks (ZIFs) was showcased. The strong interaction of Mn and Co contributes to the production of rich Mn3+ and Co3+ content (Mn4+ + Co2+ → Mn3+ + Co3+; Mn2+ + Co3+ → Mn3+ + Co2+). Compared with W/Co3O4, the Mn addition can increase the accessibility of active sites, induce more oxygen vacancies, acid sites and defects formation at the interfacial regions, promote the adsorption and activation of NH3 and NO, resulting in a 10–50 % higher NOx conversion at the 100−300 °C under 40,000 h−1. More encouragingly, experimental results suggested that the Mn-containing catalyst also exhibits much better tolerance against SO2, H2O, and HC than the Mn-free catalyst. This work demonstrates that guest@host POM@ZIF-functionalized derivative materials possess promising application perspective for low-temperature NOx reduction.