Selective Catalytic Reduction Research Articles

Enabling Wide-Temperature Selective Catalytic Reduction of NOX via Modulating Redox Ability of Mn-Based Catalysts

Enabling Wide-Temperature Selective Catalytic Reduction of NO_X via Modulating Redox Ability of Mn-Based Catalysts

Modulating the Activity and SO2 Resistance of α-Fe2O3 Catalysts for NH3-SCR of NOx via Crystal Facet Engineering.

The development of Fe-based catalysts for the selective catalytic reduction of NOx by NH3 (NH3-SCR of NOx) has garnered significant attention due to their exceptional SO2 resistance. However, the influence of different sulfur-containing species (e.g., ferric sulfates and ammonium sulfates) on the NH3-SCR activity of Fe-based catalysts as well as its dependence on exposed crystal facets of Fe2O3 has not been revealed. This work disclosed that nanorod-like α-Fe2O3 (Fe2O3-NR) predominantly exposing (110) facet performed better than nanosheet-like α-Fe2O3 (Fe2O3-NS) predominantly exposing (001) facet in NH3-SCR reaction, due to the advantages of Fe2O3-NR in redox properties and surface acidity. Furthermore, the results of the SO2/H2O resistance test at a critical temperature of 250 °C, catalytic performance evaluations on Fe2O3-NR and Fe2O3-NS sulfated by SO2 + O2 or deposited with NH4HSO4 (ABS), and systematic characterization revealed that the reactivity of ammonium sulfates on Fe2O3 catalysts to NO(+O2) contributed to their improved catalytic performance, while ferric sulfates showed enhancing and inhibiting effects on NH3-SCR activity on Fe2O3-NR and Fe2O3-NS, respectively; despite this, Fe2O3-NR showed higher affinity for SO2 + O2. This work set a milestone in understanding the NH3-SCR reaction on Fe2O3 catalysts in the presence of SO2 from the aspect of crystal facet engineering.

Synthesis‐structure‐catalysis relations in CHA zeolites applied for selective catalytic reduction of NOx with ammonia

Microporous aluminosilicate zeolites are useful industrial catalysts. However, their hydrothermal synthesis is a multistep process with complicated and unclear reactions, limiting their rational functional design. Herein, we compare the formation pathway and the structural and catalytic properties of several CHA zeolites to obtain fundamental knowledge for intentionally controlling the catalytic function of zeolites. Three CHA zeolites were synthesized using different starting silica/alumina sources in the presence of tetraethylammonium hydroxide as an inexpensive organic structure‐directing agent. FAU zeolite and an amorphous synthesis gel prepared using two different methods were used as starting materials. The obtained CHA zeolites were applied for exhaust gas purification (selective catalytic reduction of NOx with ammonia, NH3‐SCR), and their structural characteristics and formation pathways were investigated using a combination of analytical methods. Stepwise gel preparation (SGP), which divides the compositional control of the amorphous synthesis gel, promotes the decomposition of the initial additive (zeolite seed), resulting in the formation of CHA zeolites with abundant micropores and paired Al sites. This structural feature obtained using the SGP method improves the catalytic durability of the NH3‐SCR reaction. The present relationship, including different crystallization phenomena, structures, and catalytic abilities, provides useful insights into rational zeolite synthesis and its application.

Simultaneous measurement of NH3 and NO by mid-infrared tunable diode laser absorption spectroscopy based on machine-learning algorithms

Accurate measurements of NH3 and NO are essential for controlling NOx emissions from coal-fired power plants, reducing ammonia slip, and improving the efficiency of selective catalytic reduction (SCR) operation. We propose a method for measuring NH3 and NO concentrations based on machine learning algorithms to address the challenges posed by overlapping interference of CO2 and H2O spectral lines in flue gas. Our approach introduces a novel method for acquiring mixture spectra for the model. Initially, we measure the spectra of individual components under different concentrations and temperatures. Subsequently, mixed spectral samples are generated by combining the measured spectra of the individual components. This approach simplifies the spectral measurement process while preserving accuracy. The particle swarm optimization support vector machine (PSO-SVM) algorithm is leveraged, providing a reliable foundation for the continuous and synchronous measurement of NH3 and NO. Upon testing, the PSO-SVM demonstrates average relative errors of 4.0 % and 0.8 % for NH3 and NO concentrations, respectively. The corresponding measurement precision is 0.05 ppm for NH3 and 0.42 ppm for NO, better than the conventional integral absorbance method. The minimum detection limit (MDL) for NH3 is 16.1 ppb at an average time of 50 s, while for NO, it is 38.4 ppb at an average time of 71 s. The methodology of this paper is expected to play an important role in reducing the influence of interfering components and improving the accuracy of field measurements.

Effect of morphology on the performance of MnOx catalysts for selective catalytic reduction of NO with NH3

Modulating the physicochemical properties of catalysts through the construction of special crystal structures or microscopic morphology provides new insights for developing high-performance low-temperature denitrification catalysts. This paper explores the effect of morphology structure on catalyst performance and identifies the dominant driving factors. The catalyst activity sequence was found to be MnOx spiny nanospheres (Mn-SNS) > MnOx nanowires (Mn-N) > MnOx nanospheres (Mn-NS) > MnOx nanoparticles (Mn-P). Among these, the Mn-SNS catalyst prepared by the hydrothermal method exhibited the best catalytic activity and the good resistance to water and sulfur. It achieved over 70% NOx conversion at 150 °C, and maintained 100% at 200–350 °C. In the presence of SO2 and H2O, the NOx conversion was maintained at 87%. The spherical structure consisting of nanospikes provides the Mn-SNS catalysts with a large specific surface area, more (Mn4++Mn3+), abundant acid sites, and stronger reducibility, thus exhibiting excellent performance through the "fast-SCR" pathway. It also inhibits oxide crystallization and provides more sites for the adsorption activation of NOx and NH3. The nanowire structures can provide a large specific surface area and a high concentration of Mn3+ and Mn4+ for MnOx catalyst. Characterization analyses revealed that the specific surface area, the ratio of (Mn4++Mn3+)/Mn, and the number of Lewis acid sites (L-NH3) are the most important factors affecting the catalytic activity. This present empirical analysis provides new ideas for designing high-performance catalysts with a large specific surface area.

Assembling copper and cerium into TNU-9-type periodic microporous organosilicas for the selective catalytic reduction of NOx by NH3

TNU-9-type periodic microporous organosilicas material containing Ce and Cu was assembled by organic-inorganic hybrid method and then calcined to acquire CuCex@PMO-TNU-9 catalyst. The effect of cerium on the structure-performance relationship was studied. The results indicated that the (CuCex@PMO-TNU-9 x = 1.0, 1.5 and 2.0) catalysts were successfully prepared, whereas CuCe2.5@PMO-TNU-9 was not successfully prepared due to the excess of the precursor resulting in the difference of hydrolysis rate between the organosilane precursor and white carbon black. The CuCe2@PMO-TNU-9 catalyst showed higher NH3-SCR activity than Cu@PMO-TNU-9, which was because that the interaction between Ce and Cu could form Cu2++Ce3+↔Cu++Ce4+ redox cycle, which promoted the oxidation of NO to NO2, forming “fast SCR” reaction. More importantly, CuCe2@PMO-TNU-9 catalyst had excellent the resistance of H2O and SO2 due to the excellent hydrophobicity of the TNU-9 zeolite and the sacrificial site Ce protecting the active site Cu.

Changes of Nitrate Activity and Byproduct Distribution Characteristics for Synergistic NOx and Dioxin Abatement over V2O5/AC Catalyst.

The simultaneous removal of NOx and dioxins has been considered an economical and effective technology of controlling multipollutant flue gas in the context of "carbon peaking and carbon neutrality". However, this technology has not yet been implemented in practical situations, because the interactive relationship between the selective catalytic reduction (SCR) reaction and dioxin catalytic oxidation lacks a deep understanding, especially on a carbon-based catalyst. In this research, the influence of NO and NH3 on the oxidation characteristics and byproducts distribution of dibenzofuran (DBF) was studied on V2O5/AC catalyst. Results indicated that NH3 has a stronger inhibition effect for DBF catalytic oxidation than NO due to obvious competitive adsorption between NH3 and DBF on the V2O5/AC catalyst. In addition, although both NO and NH3 inhibit the complete degradation of DBF, their effects on the byproduct distribution are not consistent. NO primarily affects the level of oxygen-containing byproducts, while NH3 primarily affects the level of alkane byproducts. Furthermore, the SCR reaction activity demonstrated a reduction when DBF was present. The occupation of V2O5 sites by DBF and its oxidizing intermediates has hindered the production of monodentate nitrate and the reactivity of bridged nitrate, resulting in a decrease in SCR activity via the L-H mechanism. This work aims to provide theoretical guidance for simultaneous removal of NOx and dioxins in industrial fumes.

An assessment of inorganic components in condensable particulate matter as a function of surface aggregation, spatial suspension state and particle size

Experimental studies assessed the removal efficiency and fine-size distribution of CPM coupled with compositional analysis across air pollution control device systems (APCDs) at an ultra-low emission (ULE) power plant. The findings indicated total CPM emissions were reduced to a minimum of 0.418mg/m3 at the Wet Electrostatic Precipitator (WESP). The Wet Flue Gas Desulfurization (WFGD) showed the highest removal efficiency (98%) across all particle sizes, notably in the ultra-micron range. Selective Catalytic Reduction (SCR) demonstrated a mere 34% overall efficiency, with a negative removal rate in the ultra-fine particle range. The WESP effectively removed CPM only in sub-micron and ultra-micron sizes, but significantly increased water-soluble ions formation in ultra-fine spatially suspended CPM (CPMspa), leading to overall negative efficiency. Thus, the removal efficiency of the ultra-fine particle range was most affected among the three particle size ranges when the flue gas went through the APCDs. Major metal elements and water-soluble ions were more readily removed by APCDs due to their surface aggregation, while the removal of trace elements like Hg and Se was limited. Reducing SO42-/NH4+ formation in SCR, and optimizing WESP spray system operations based on flue gas components are essential steps in controlling CPM concentration in ULE power plants.

An amperometric high-temperature ammonia sensor based on a BaCo0.4Fe0.4Zr0.1Y0.1O3-δ triple conductor

Selective catalytic reduction (SCR) utilizing urea hydrolysis to generate ammonia (NH3) is the most efficient technology to reduce the emission of nitrogen oxides (NOx). NH3 detection is crucial in the closed-loop feedback system for the precise urea injection. In this work, a high-temperature NH3 sensor using a BaZr0.8Y0.2O3-δ (BZY) proton conductor as the electrolyte and a BaCo0.4Fe0.4Zr0.1Y0.1O3-δ (BCFZY) H+/e–/O2– triple conductor as the sensing electrode (SE) is reported. The effect of the micromorphology of the BCFZY SE on the sensing performance is investigated by varying the sintering temperature of SE. The sensor shows high sensitivity to NH3 with response currents of 0.39, 1.31, 3.03, and 1.81 μA/ppm at 350, 400, 450, and 500 °C, respectively. Furthermore, the sensor shows excellent selectivity and repeatability. This work demonstrates that the BCFZY based sensor has great potential for the high-temperature NH3 detection.

Revealing the two distinctive roles of HY zeolite in enhancing the activity and durability of manganese oxide-zeolite hybrid catalysts for low-temperature NH3-SCR

Recently, metal oxide-zeolite hybrid systems have shown promise in enhancing catalytic performance in low-temperature selective catalytic reduction (SCR), but not much is known as to mechanistic details. The purpose of this study is to examine fluctuations in low-temperature activity contingent upon the presence or absence of zeolite and to elucidate a dual functional mechanism of mixed zeolite in improving the catalytic performance of MnOx, which is closely related to inter-particle diffusion of nitrite and nitrate species from MnOx to zeolite. Firstly, strong Brønsted acid sites on zeolite demonstrate a significantly faster reduction of diffused nitrite species compared to Brønsted/Lewis acid sites on MnOx. More importantly, we discovered that zeolite prevents ammonium nitrate deposition by absorbing and decomposing diffused nitrate species from MnOx. Such distinct interaction between zeolite and both nitrite and nitrate species clarified here will be of great promise in designing future hybrid catalytic materials for low-temperature NH3-SCR reactions.

Study on performance and water deactivation mechanism of low-temperature denitrification catalyst in high-humidity flue gas

To address water poisoning issues of Selective Catalytic Reduction (SCR) denitrification catalysts in high-humidity flue gas, this study synthesized catalysts including Co–Mn/TiO2, Co–Mn–Ce/TiO2, Co–Mn–Ce/TiO2–Si, and Co–Mn–Ce/TiO2 (stearic acid). The activity of the catalysts at low temperatures and high humidity (140–180 °C, 0–35 vol%) was evaluated. Furthermore, the characterization of the most effective of these (the Co–Mn–Ce/TiO2 (stearic acid) catalyst) was performed. The results revealed distinct mechanisms of water poisoning under high- and low-humidity conditions. Under high humidity, the dissolution of water molecules affected the catalyst structure and thereby, resulted in reduced dispersibility of the active components. Conversely, at low humidity, the dissolution effect was relatively marginal, which resulted in a more stable catalyst structure. High-humidity flue gas reduced the catalyst acidity and thereby, hindered NH3 adsorption. Meanwhile, low-humidity flue gas had a lesser impact on the catalyst. High-humidity flue gas hinders the conversion of Co ions in Co–Mn–Ce/TiO2（stearic acid ) to higher oxidation states and reduced Ce4+ to Ce3+. This resulted in decreased Mn4+ on the catalyst surface and reduced chemisorbed oxygen (Oa). This, in turn, affected the adsorption and storage of oxygen by the catalyst.

TiO2 modified limonite for selective catalytic reduction of NO from cement kiln flue gas with NH3

Limonite was used as a precursor and TiO2 as a modifier to synthesize TiO2/Limonite composites through the wet impregnation method. The influences of the TiO2 doping amount, the calcination temperature on the denitration efficiency and the structure and properties of composites were systematically studied. The results showed that the modified catalyst over the Ti/Fe mass ratio was 0.07 and the calcination temperature was 300°C exhibited excellent catalytic activity, good stability, and remarkable resistance to water and sulfur dioxide within reaction temperature of 100 ∼ 240°C. When NO initial concentration was 0.05 % and gas hourly space velocity (GHSV) was 36,000 h−1 and the reaction temperature was 130°C, the NO conversion efficiency reached 100 %, and the N2 selectivity was 99.6 %. When the catalyst was exposed to 10 %H2O at 150°C, it maintained a 100 % NO conversion efficiency. In the presence of 10 %H2O and 50 ppm SO2 at 200°C, the NO conversion efficiency remained at 100 %. The TiO2/Limonite catalyst possessed improved performance due to the introduction of the anatase TiO2, which led to more lattice defects, weak Lewis acid sites, and higher adsorbed oxygen mobility.

Investigation of Co–Mn–Ce Ternary Composite Oxide Catalyst for Low-Temperature Selective Catalytic Reduction of NOx with NH3

Investigation of Co–Mn–Ce Ternary Composite Oxide Catalyst for Low-Temperature Selective Catalytic Reduction of NOx with NH3

Promoted catalytic property of Cu/SSZ-13 by introducing a minority of Mn for NO removal from diesel engine exhaust

The Cu-exchanged SSZ-13 with the small-pore chabazite framework is considered as a highly efficient catalyst for selective catalytic reduction of NO with NH3 (NH3-SCR). In order to further improve the catalytic property, a series of Mn ion-assisted Cu/SSZ-13 powder catalysts were prepared by co-exchange method and stepwise exchange method. It is found that the NH3-SCR activity, N2 selectivity, hydrothermal stability and sulfur resistance of Cu/SSZ-13 are promoted by introducing a minority of Mn (0.15%–0.23%(mass)) through co-exchange method. Characterization results revel that the Cu,Mn co-exchange enables the higher amounts of Cu2+ active sites, the abundant medium strong and strong acid, the optimized ratio of lewis acid to Brønsted acid, etc., which are required for a good NH3-SCR catalytic property over broad temperature range and under harsh working environment. Moreover, a monolithic catalyst was prepared by impregnating a cordierite ceramic support into the coating slurry containing the optimized CuMn/SSZ-13 powder. The diesel engine bench tests show that Cu,Mn co-exchange gives the monolith catalyst a better catalytic property than commercial catalysts. This work provides an important guidance for the rational design of secondary-ion-assisted zeolites applied in NH3-SCR.

Effect of sulfation on the catalytic performance of Mn-Co composite oxide catalyst for the selective catalytic reduction of NOx by NH3

The effect of sulfation on the catalytic performance of Mn-Co composite oxide catalyst for the selective catalytic reduction of NOx by NH3 (NH3-SCR) has been investigated. Different concentrations of SO2 have been used to sulfate Mn-Co composite oxide catalyst. The catalyst sulfated with 30 ppm SO2 showed the widest activity temperature window, over which 80% NOx conversion was obtained in the temperature range of 80–350 °C. The sulfation leads to the appropriate redox property of Mn-Co composite oxide, thus improving the N2 selectivity. Meanwhile, the sulfation contributes to the generation of more Brønsted acid sites, which is crucial for the enhanced activity. In situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS) demonstrated that the adsorbed NH3 species on both Lewis acid and Brønsted acid sites, monodentate nitrite, bidentate nitrate and cis-nitrite species are the reactive intermediates in the NH3-SCR reaction. This study provides an idea for the regulating the activity temperature window of NH3-SCR catalyst to adapt to its practical application.

Designing ammonia oxidation catalysts via physical mixing of Pt/SiO2 and Cu/ZSM-5

Ammonia (NH3) is emerging as a carbon-neutral fuel alternative; however, its use poses environmental and health risks due to NH3 slip. The NH3-selective catalytic oxidation (NH3-SCO) process, which converts NH3 into N2 and H2O, offers a solution. However, it faces challenges with respect to the formation of byproducts, particularly N2O and NOx. This study focuses on designing NH3-SCO catalysts to enhance low temperature NH3 conversion efficiency while minimizing undesired byproducts. Pt/SiO2 catalysts were synthesized with adjusted Pt particle sizes to improve the NH3-SCO activity and were physically mixed with Cu/ZSM-5 to overcome the low N2 selectivity of Pt-based catalysts by utilizing the selective catalytic reduction (SCR) ability of Cu/ZSM-5. Pt1Cu3 catalyst, a physical mixture of Pt/SiO2 and Cu/ZSM-5 in a 1:3 mass ratio, was found to be the most effective, achieving complete NH3 oxidation at 250 ℃ while maintaining a high N2 selectivity of approximately 80%. Further investigation revealed that the performance of the Pt1Cu3 catalyst was significantly influenced by the arrangement and physical proximity of the Pt/SiO2 and Cu/ZSM-5 catalysts, with a closely contacted mixture showing synergistic effects that enhanced activity and selectivity. These results suggest that the Pt1Cu3 catalyst offers a promising solution for NH3 emission control by utilizing a balanced approach that combines SCO and SCR reactions.

Activity of CuCoCe layered double hydroxides catalysts and mechanism for C3H6-SCR

CuxCoyCez-LDH prepared with layered double hydroxides (LDHs) as precursors was calcined to form CuxCoyCezO catalysts which were experimentally investigated for the selective catalytic reduction of NO by C3H6 (C3H6-SCR) in a fixed bed micro-reactor in the presence of O2. The physical–chemical properties of the catalysts were characterized and analyzed with respect to the SCR reactivity. In situ DRIFTS study was conducted to investigate the intermediate species during the SCR reaction. Results showed that NO conversion was as high as 95 % at 225 °C over Cu0.21Co0.48Ce0.31O catalyst. The excellent activity of the catalyst could be attributed to the synergistic effect between Cu, Co, and Ce. The XRD results showed that the synergistic effect between the metals was because of the formation of the solid solution between Cu, Co, and Ce, which promoted the interaction and dispersion of the three active components. EDS mapping further proved this point. According to the XPS data, Cu and Co had a redox reaction that increased the number of oxygen vacancies favorable for NO adsorption and dissociation. The redox properties between Cu and Co was further confirmed to improve the catalytic activity by H2-TPR. Additionally, the results of BET and NH3-TPD demonstrated that the SCR catalytic activity was promoted by the right quantity of acidic sites and the specific surface area. In situ DRIFTS experiments provided a mechanism for the C3H6-SCR reaction on the catalyst and confirmed the formation of reaction intermediates such as bidentate and monodentate nitrate, formate, and acetate.

Design of dual-ligand coordination in metal organic frameworks for breaking the seesaw effect between de-NOx activity and N2 selectivity

In the selective catalytic reduction (SCR) of NOx with NH3, a catalyst usually exhibits a seesaw effect on de-NOx activity and N2 selectivity at low temperatures. Herein, we designed metal-organic frameworks (MOFs) with dual-ligand coordination to regulate the electronic and morphological structure for a breakthrough of the seesaw effect. The developed catalyst attained a noteworthy NOx conversion exceeding 90% within 60–330 ℃ with increased N2 selectivity. The dual-ligand coordination leads to more defects and a more uniform electron distribution for delocalization of electrons, thereby improving de-NOx activity. Furthermore, the dual-ligand coordination manifests a Si-O-Mn bond for amplifying both de-NOx activity and thermal stability. Additionally, the dual ligands and Mn produce a hollow sea-urchin-like morphology with more exposed active sites for concentrating reactants and intermediates to improve electron transfer efficiency in N2 selectivity. This work clarifies the mechanism of dual-ligand regulation for electron-morphology to simultaneously enhance de-NOx activity and N2 selectivity.

In-situ interzeolite transformation synthesis Cu-SSZ-13 from coal fly ash-derived zeolite for NH3-SCR reaction

Cu-SSZ-13 catalyst has excellent performance for removing NOx. In this study, the in-situ inter-zeolite transformation (IZT) method was proposed to prepare Cu-SSZ-13 catalyst. The coal fly ash-derived zeolite acted as a raw material rather than the chemical silicon and aluminum source. A series of catalysts were prepared using the in-situ IZT method with different ratios of the two template agents. The NO conversion of Cu-SSZ-13 catalysts was above 90 % within the temperature range of 200–700 °C, whereas the N2 selectivity was maintained at about 100 %. The as-synthesized catalysts had higher conversion rates for Si and Al, higher copper loading and more isolated Cu2+. The selective catalytic reduction (SCR) reaction mechanisms of Cu-SSZ-13 catalyst prepared using the in-situ IZT method followed both the Eley-Rideal (E-R) mechanism and the Langmuir-Hinshelwood (L-H) mechanism, though it was mainly based on the E-R reaction. In this study, the Cu-SSZ-13 catalysts were synthesized using coal fly ash based zeolite in one step. This study further improved the synthesis process route from coal based solid waste to SCR catalyst, shortened the preparation cycle, and improved catalyst performance.

A Bayesian network development methodology for fault analysis; case study of the automotive aftertreatment system

This paper proposes a structured methodology for generating a Bayesian network (BN) structure for an engineered system and investigates the impact of integrating engineering analysis with a data-driven methodology for fault analysis. The approach differs from the state of the art by using different initial information to build the BN structure. This method identifies the cause-and-effect relationships in a system by Causal Loop Diagram (CLD) and based on that, builds the Bayesian Network structure for the system. One of the challenges in identifying the root cause for a fault is to determine the way in which the related variable causes the fault. To deal with this challenge, the proposed methodology exploits Dynamic Fault Tree Analysis (DFTA), CLD and the correlation between variables. To demonstrate and evaluate the effectiveness of the presented method, it is implemented on the data-driven methodology applied to the automotive Selective Catalytic Reduction (SCR) system and the obtained results have been compared and discussed. The proposed methodology offers a comprehensive approach to build a BN structure for an engineered system, which can enhance the system's reliability analysis.