Selective Catalytic Reduction Catalyst Research Articles

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.

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.

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

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.

Pilot-tests of the coal-fired power plant indirect coupling with multi-source organic solid waste incineration technology

The production of organic solid waste is increasing as the development of society. However, the investment of waste incineration power plant is very high and the thermal efficiency is very low. At the same time, the load of coal-fired power plant is suppressed due to the carbon neutralization policy. Therefore, using the existed coal-fired power plant to co-process the organic solid waste is a feasible method. In this paper, a coal-fired power plant indirect coupling with waste incineration technology based on flue gas circulation was proposed and studied on a 100 kW pilot-test bench. In this technology, the polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) was reduced by a three stages controlling method, which adopts the blending of multi-source organic wastes, high-temperature decomposition and selective catalytic reduction (SCR) catalyst decomposition, simultaneously. The effects of waste incineration coupling, replacement ratio of coal, and flue gas circulation on the combustion and pollutant emission characteristics of the system were studied. The experimental results indicate that the waste incineration coupling has minor influence on the temperature distribution and the toxicity of fly ash of the coal-fired furnace. The NO, HCl, and PCDD/Fs concentrations of flue gas of coal-fired furnace generally decrease as the replacement ratio of coal increases, while the SO2 concentration increases. With the help of three stages controlling method or the flue gas circulation, the PCDDFs concentration of the flue gas of coal-fired furnace can be much lower than 0.1 TEQ ng/Nm3.

Promoting effect of polyoxometallic acid modification on the NH3-SCR performance of Mn-based catalysts

The strong oxidation capabilities of Mn sites render Mn-based catalysts showing high activities of selective catalytic reduction (SCR) at temperatures < 250℃, but simultaneously lead to the generation of by-product N2O with strong greenhouse effect. The activity-N2-selectivity trade-off was a prevalent observation in the development of Mn-based SCR catalysts. Here, a polyoxometallic acid enhancement strategy was devised to simultaneously promote the N2 selectivity and low-temperature SCR (LT-SCR) activity of Mn-based metal oxide catalysts, where the introduction of uniformly dispersed phosphomolybdic acid (HPMo) tuned the oxidation capabilities and enhanced NH3 adsorption-storage capability of catalysts. The combination of transient reaction, in-situ DRIFTS analysis and DFT calculations revealed that the main origin of N2O on the Mn-based catalysts was the deep oxidation of NH3, which was inhibited by the interaction between HPMo and Mn sites. Additional NH3 molecules adsorbed by the abundant acid sites supplied by HPMo further facilitated the SCR reaction. This strategy could guide the design of high-activity and high-selectivity LT-SCR catalysts for industrial denitration.

Unraveling the Effect of Mo Dopant in Fe2O3 Catalyst for Selective Catalytic Reduction of Nitric Oxide with NH3

Unraveling the Effect of Mo Dopant in Fe₂O₃ Catalyst for Selective Catalytic Reduction of Nitric Oxide with NH₃

Structure and activity relationships of AMn2O4 (A = Mg and Zn) spinels in selective catalytic reduction of NOx with NH3

Mn-based spinel as a catalyst for low-temperature selective catalytic reduction with ammonia (NH3-SCR) has been widely studied. However, most researchers have focused on double transition metal Mn-based spinel and the reports about doping with non-transition metal are not common. Herein, Mg2+ and Zn2+ with similar ionic radii were used to prepare high purity MgMn2O4 and ZnMn2O4 (named MMO and ZMO) to study their structure and activity relationships in NH3-SCR. It was found that the denitration performance of the two showed significant differences at low temperature despite have a very similar crystal structure. A series of characterization methods and first-principles calculations demonstrates that the relatively weak bonding strength and basic adsorption sites of MMO catalyst are the key factors contributing to its superior reactivity at low temperatures. This work provides novel insights and ideas in comprehending the catalytic function of non-transition metal-doped Mn-based spinels in NH3-SCR reactions.

Enhancement of low-temperature activity of γ-Fe2O3-modified V2O5-MoO3/TiO2 catalysts for selective catalytic reduction of NOx with NH3

In this study, a series of γ-Fe2O3-modified V2O5-MoO3/TiO2 (VMT) catalysts was prepared by wet impregnation method. The γ-Fe2O3-modified catalysts exhibited excellent catalytic performance, and 1.25 wt% γ-Fe2O3 content improved the deNOx efficiency at 150 °C from 54% (unmodified VMT catalyst) to 84% (modified catalyst). BET, XRD, XPS, NH3-TPD, H2-TPR, and in situ DRIFTs were employed to characterize the physicochemical properties and reaction mechanisms of the catalysts. The introduction of γ-Fe2O3 increased the V5+/V4+ ratio, surface chemisorbed oxygen content, redox ability, and a number of acid sites in the prepared catalysts. XPS confirmed the addition of γ-Fe2O3 introduced new charge transfer pathways (Fe3+/Fe2+ ↔ V5+/V4+). In situ DRIFTs suggested that the addition of γ-Fe2O3 to the catalyst significantly increased the adsorption capacity of catalyst for NH3 and NOx, while also exerting a strong activating effect on the adsorbed NH3. Furthermore, selective catalytic reduction over the VMT and 5PEG@1.25Fe-VMT catalysts followed the Eley-Rideal (E-R) mechanism. At temperatures above 200 °C, the 5PEG@1.25Fe-VMT catalyst also followed the Langmuir-Hinshelwood (L-H) mechanism.

Unlocking the Potential of Metal-Doping Fe2O3/Rice Husk Ash Catalysts for Low-Temperature CO-SCR Enhancement.

Transition metal oxides are efficient bifunctional catalysts for the selective catalytic reduction (SCR) of nitrogen oxides (NOx) using CO. Nonetheless, their poor activity at lower temperatures constrains broader industrial application. Herein, we propose an optimized Fe2O3-based catalyst through strategic metal doping with Cu, Co, or Ce, which engenders a harmonious balance for the synergistic removal of CO and NOx. Among the developed catalysts, Co-doped Fe2O3, supported by rice husk ash, demonstrates superior low-temperature CO-SCR activity, achieving CO and NOx conversion ratios and N2 selectivity above 98.5% at 100-500 °C. The enhanced catalytic performance is attributed to the catalyst's improved redox properties and acidity, engendered by strong Fe-Ox-Co interactions. Furthermore, the CO-SCR reaction adheres to the Langmuir-Hinshelwood and Eley-Rideal mechanisms. Our findings shed light on the future industrial application of low-temperature CO and NOx near-zero emission technology and provide a strategy for the design of low-cost SCR catalysts.

Multi-objective optimization of Fe-based SCR catalyst on the NOx conversion efficiency for a diesel engine based on FGRA-ANN/RF

With the development of industrial level and the increasingly strict emission regulations, selective catalytic reduction (SCR) system is one of the important ways to control NOx emissions from diesel engines. In this study, the effects of intake pressure on pressure and NOx conversion efficiency before and after catalyst were investigated at different loads. In order to improve the SCR efficiency, a multi-objective prediction method based on FGRA-ANN/RF was developed for SCR systems, where the predicted output parameters (the front and back section temperatures of the catalyst, the pressure difference, and the instantaneous catalytic efficiency) and the decision variables (the engine operating parameters). Firstly, the sensitivity analysis of the multi-objective inputs obtained from the ETC condition experiments is performed by the fuzzy grey relation method (FGRA) to select the high sensitivity parameters. Then, the prediction was carried out by artificial neural network (ANN) as well as the improved random forest (RF). The experimental results showed that the evaluation index R2 of RF was generally greater than 0.92 and the improved random forest method had high accuracy and robustness. It is valuable for solving SCR industrial simulation and reducing the hysteresis of ammonia injection response.

Theoretical study on K poisoning resistance of M-doped Ce/TiO2 (001) surface (M=Cu, Co, Zr, Sb, Mo, Nb, W)

Enhancing the resistance of SCR (Selective Catalytic Reduction) catalyst to K poisoning can be effectively achieved through modification. This study investigated the impact of transition metal modification on improving the ability of Ce/TiO2 (CT) catalysts to resist K poisoning by DFT (Density functional theory) calculations. Mo-, Nb-, and W-doping could effectively suppress the adsorption of K. Ov (oxygen vacancy) formation and hydrogenation reactions were both facilitated due to the modification of Cu, Co and Sb. The Cu-doping had a significant contribution to the adsorption of NH3 and NO, and showed the best resistance to K poisoning in the adsorption of reactive species. Additionally, Cu-doping decreased the energy barriers for NH3 dehydrogenation, NH2NO generation and decomposition, and NO2 formation on CT catalyst, and weakened the inhibition effect of K on the above elementary reactions. Consequently, this provided an effective improvement in the k-poisoning tolerance of the CT catalysts.

Modulating the acidity and reducibility of FeMn/TiO2 to boost the low-temperature selective catalytic reduction of NOx

The design and fabrication of selective catalytic reduction (SCR) catalyst with ultra-low-temperature activity is diligent, however, remains challenging hitherto. Herein, a variety of TiO2-based catalysts with various Fe/Mn ratios were fabricated using a coprecipitation technique and tested for SCR of NOx with ammonia. The experimental results demonstrate that the Fe/Mn ratio considerably affects the acidity, redox property and thereafter the NH3-SCR behavior of FeMn/TiO2 catalysts. Therein, Fe0.3Mn0.7/TiO2 exhibits the broadest activity temperature window from 75 to 210 °C because of its more reactive oxygen species and higher Mn4+ ratio on the catalyst surface, leading to improved oxidation performance and surface acidity, thereby promoting the generation of active NO2 and HONO intermediates, and thereafter enabling the catalyst to adsorb more NH3 to generate active nitrate species and increasing the NH3-SCR performance. Further increasing or decreasing the Fe/Mn ratio would downgrade the SCR performances of corresponding catalysts due to the mismatch between acidity and redox ability, which inhibits the formation of active NO2 and HONO intermediates. In-situ DRIFTS results further illustrate that the SCR of NOx over FeMn/TiO2 catalysts follow both the L-H and E-R mechanisms at the low temperature, however, the types of active nitrates flourish at high temperatures, primarily via the E-R mechanism.

Promotional effect of aluminum doping on the sulfated Fe2O3 catalyst in selective catalytic reduction of NO with NH3

Promotional effect of aluminum doping on the sulfated Fe2O3 catalyst in selective catalytic reduction of NO with NH3

Promotion of Cu/Ce supported red mud for NO removal from low and medium temperature flue gas

Red mud is a solid waste in aluminum industry and has been proven to be an efficient alternative to NOx selective catalytic reduction (SCR) catalysts. Acid washing treatment to red mud can improve its alkalinity and surface properties, and increase the conversion rate of NOx. In this paper, Cu, Ce, and Cu/Ce was supported on acid washed red mud and NOx catalytic conversion performance on metal modified red mud catalysts was studied. The research results indicate that Cu+ and Cu2+ in the Cu supported catalyst effectively promote NO conversion rate of red mud in low-temperature (200–300 °C) flue gas, reaching a maximum of 90.7%; Ce3+ and Ce4+ in Ce supported catalysts effectively promote the NO conversion rate of red mud in flue gas at 200–400 °C, reaching a maximum of 94.0%; Cu/Ce supporting exhibits better NO conversion rate than single metal supported catalysts at low-temperatures, the optimal Cu:Ce ratio for supporting is 1:1; and also exhibits better NO conversion rate than Cu supported catalysts at high-temperature (300–400 °C), reaching a maximum of 95.5%. The reason may be that under the synergistic effect of Cu/Ce, ACRM-Cu1Ce1 has stronger low-temperature redox ability, higher weak acidic peaks, higher average oxidation state of Fe ions, and higher Cu+ content.

Insight into the Alkali Resistance Mechanism of FeMoTiOx Catalysts for NH3 Selective Catalytic Reduction of NO: Self-Defense Effects of MoOx for Alkali Capture.

The deactivation of selective catalytic reduction (SCR) catalysts caused by alkali metal poisoning remains an insurmountable challenge. In this study, we examined the impact of Na poisoning on the performance of Fe and Mo co-doped TiO2 (FeaMobTiOx) catalysts in the SCR reaction and revealed the related alkali resistance mechanism. On the obtained Fe1Mo2.6TiOx catalyst, the synergistic catalytic effect of uniformly dispersed FeOx and MoOx species leads to remarkable catalytic activity, with over 90% NO conversion achieved in a wide temperature range of 210-410 °C. During the Na poisoning process, Na ions predominantly adsorb on the MoOx species, which exhibit stronger alkali resistance, effectively safeguarding the FeOx species. This preferential adsorption minimizes the negative effect of Na poisoning on Fe1Mo2.6TiOx. Moreover, Na poisoning has little influence on the Eley-Rideal reaction pathway involving adsorbed NHx reacting with gaseous NOx. After Na poisoning, the Lewis acid sites were deteriorated, while the abundant Brønsted acid sites ensured sufficient NHx adsorption. As a benefit from the self-defense effects of active MoOx species for alkali capture, FeaMobTiOx exhibits exceptional alkali resistance in the SCR reaction. This research provides valuable insights for the design of highly efficient and alkali-resistant SCR catalysts.

Enhancing resistance to CaO&PbO poisoning of CeO2/TiO2 NH3-SCR catalyst via hybrid with SO42−/ZrO2: Dual functions of SO42−/ZrO2

Catalyst deactivation caused by the co-poisoning of alkaline earth metals (CaO) and heavy metals (PbO) is still a problem in the NH3 selective catalytic reduction (SCR) of NOx in flue gas. In this work, a hybrid catalyst (Hybrid-CT) was being synthesized by grinding CeO2/TiO2 (CT) catalyst and SO42−/ZrO2 to evaluate the poisoning tolerance. It shown that Hybrid-CT exhibited a higher tolerance against CaO&PbO poisoning compared with CT. Under the co-poisoning of 2.5 wt% CaO and 2.5 wt% PbO, the NOx conversion of Hybrid-CT catalyst could approach to 100 % at 350 °C. Whereas, the NOx conversion of CT was only 66.3 % under the same condition. A series of characterizations suggested that the SO42−/ZrO2 could inhibit the CaO&PbO poisoning. Once the CaO&PbO present on the surface of Hybrid-CT catalyst, SO42− could convert CaO&PbO into CaSO4&PbSO4 with less toxic, which could protect the redox site and acid site of the CeO2/TiO2. Furthermore, the ZrO2 released from SO42−/ZrO2 could serve as a promoter, enhancing the acid performance of CeO2/TiO2 catalysts. Moreover, SO42−/ZrO2 could also reduce the passive effect of CaO&PbO on nitrate oxide. This work provides a simple and novel way to improve the resistance to CaO&PbO of Ce-based SCR catalysts.

A green approach for preparation of MnFeTi Low-temperature NH3-SCR catalysts: utilizing spent V2O5–WO3/TiO2 Catalysts

V2O5–WO3/TiO2 catalysts are commonly used in industry to remove nitrogen oxides. However, spent V2O5–WO3/TiO2 are hazardous solid waste, and their improper disposal can lead to water and soil pollution risks. This study proposes a waste-to-resource approach that promotes the safe disposal of spent catalysts while reducing the production cost of denitrification catalysts. Specifically, vanadium-free low-temperature selective catalytic reduction catalysts are synthesized using spent catalysts. The optimized catalyst, named MnFeTi-22, exhibits a broad temperature activity range, with NO conversion exceeding 96 % from 100 to 300 °C. Even with 5 % H2O, the catalyst maintains a 95 % NO conversion (at approximately 200 °C). Characterization results confirm that the loading of TiO2 recycled from spent catalysts onto MnFe significantly optimizes the distribution of active species. Furthermore, TiO2 can adjust the distribution of acidic sites and the quantity of surface-adsorbed oxygen, promoting electron transfer between Mn4+/Fe2+ and Mn3+/Fe3+.

TiO2 recovered from spent selective catalytic reduction catalysts as anode material for lithium-ion batteries

Environmental protection and sustainable development are among the most severe problems in the world today. Spent selective catalytic reduction (SCR) catalysts are recognized as hazardous waste. Here, the TiO2, which accounts for nearly 80% of spent SCR catalysts, is recovered by the alkaline leaching method, and performed higher electrochemical performances than commercial TiO2 products for anode materials of Lithium-ion batteries. W, V, Si, and Al leaching rates are 40.04%, 89.59%, 61.64%, and 11.57%, respectively. A combination of density functional theory (DFT)--based calculations and experiments revealed that trace doping of Al is beneficial to the electrochemical performance of the cell, which helps us tune the Al content in the obtained materials. On this basis, the regenerated TiO2 anode materials with graphene (GR) materials are synthesized to improve the electrochemical performance, and the specific capacity of the recycled TiO2 is 188.5 mAh·g−1 after 500 cycles, and that of the regenerated TiO2/GR is the highest at 275.2 mAh·g−1. Finally, an environmental assessment of this recycling process is also carried out, human toxicity potential, CO2 gas emissions, NMVOC gas emissions, and SO2 gas emissions in this work are reduced by nearly 86.9%, 87.0%, 92.5%, and 87.0% compared with commercial sol-gel synthetic method. This work highlights the significance of recovery for preparing new energy storage materials from secondary resources.

Low-cost Co–Al spinel and M–Co–Al (M = Fe and Ce) catalysts for selective catalytic reduction of NOx with NH3

Low-cost Co–Al spinel and M–Co–Al (M = Fe and Ce) catalysts for selective catalytic reduction of NOx with NH3