Search

The effects of four distinct zinc species (ZnCl2, Zn(NO3)2, ZnSO4, and ZnCO3) on a Mn-Ce co-doped CuX (MCCX)catalyst were investigated and contrasted in the low-temperature NH3-SCR process. Aqueous solutions of ZnCl2, Zn(NO3)2, ZnSO4, and ZnCO3 were used to poison the catalysts. The catalytic activity of all catalysts was assessed, and their physicochemical properties were studied. There was a notable drop trend in catalytic activity in the low temperature range (200 °C) after zinc species poisoning on MCCX catalyst. Interestingly, ZnSO4 and ZnCO3 on MCCX catalyst had more serious effect on catalytic activity than Zn(NO3)2 and ZnCl2 from 150 °C to 225 °C, in which NO conversion of the MCCX-Zn-S and MCCX-Zn-C catalysts dropped about 20–30% below 200 °C compared with the fresh MCCX catalyst. The zeolite X structure was impacted by Zn species doping on the MCCX catalyst, and the Zn-poisoned catalysts had less acidic and lower redox ability than fresh Mn-Ce/CuX catalysts. Through the results of in situ DRIFTS spectroscopy experiments, all catalysts were governed by both Langmuir–Hinshelwood (L–H) and Eley–Rideal (E–R) mechanisms, and the possible mechanism for poisoning the Mn-Ce/CuX catalyst using various zinc species was revealed. [ABSTRACT FROM AUTHOR]

[Display omitted] Due to the accumulation of heavy metal compounds produced by the sintering process in steel industry, the catalysts used for low-temperature selective catalytic reduction of NO with NH 3 (NH 3 -SCR) might be seriously deactivated. In this work, the deactivation effect of PbCl 2 , Pb(NO 3) 2 , and PbSO 4 on Mn-Ce activated carbon supported catalyst for low-temperature NH 3 -SCR of NO was investigated and compared. Poisoned catalysts were provided by impregnating fresh catalysts with Pb(NO 3) 2 , PbSO 4 and PbCl 2 aqueous solutions, respectively. Deactivation could be observed on the poisoned samples, and the deactivation degree was following PbCl 2 > PbSO 4 > Pb(NO 3) 2. The catalytic activities of all samples were tested, and the physicochemical properties of fresh and poisoned catalysts were assessed. PbCl 2 caused the most severe deactivation of the catalyst, owing to its poor redox property and surface acidity. Cl- could also react with Mn active sites to form -O-Mn-Cl bonds, resulting in additional acid sites, although these newly generated sites were not reactive in NH 3 -SCR reaction process. PbSO 4 exhibited moderate poisoning effect due to the addition of SO 4 2-, which created new Brønsted acid sites, facilitating the NH 3 adsorption and NO reduction. Pb(NO 3) 2 had the least poisoning impact on the catalyst due to the NO 3 –, promoting the NH 3 activation. The in situ DRIFTS results revealed that NH 3 -SCR reaction over all samples was governed by Eley-Rideal (E-R) and Langmuir-Hinshelwood (L-H) mechanism, and did not change due to the lead poisoning. Finally, a possible mechanistic model for different lead salts poisoning over Mn-Ce/AC catalyst was proposed. [ABSTRACT FROM AUTHOR]

• Al 2 O 3 promoted the catalytic activity of Pb-poisoning MC/AC catalyst effectively. • Redox property and surface acidity were inherent motivation of catalytic activity. • Both E-R and L-H pathways occurred on fresh and poisoned catalysts. • Possible mechanism model of Al 2 O 3 on anti-PbCl 2 over MC/AC catalyst was proposed. Lead salts, as a heavy metal species, caused serious damage for the activity and operation lifetime of SCR catalysts. Al-decorated Mn-Ce/AC catalyst was synthesized using the impregnation method to investigate the anti-Pb poisoning ability of Al 2 O 3 on Mn-Ce/AC catalyst. The addition of Al expressed a significant promotion on activity of MC/AC catalyst in both fresh and poisoned states. XRD analysis confirmed that Al oxide confined the crystallization of active MnO 2 over the poisoned catalysts, contributing to the dispersion of components. From the morphology, Al doping increased the aggregation of PbCl 2 , which released more active sites and further restrained the negative effect of PbCl 2. More abundant of Mn4+ and surface oxygen with adding Al was in favor of the redox circle and the activation of reactants. The enhanced surface acidity and redox property served as the chemical motivations for the anti-PbCl 2 ability of catalysts. In situ DRIFTS demonstrated that all catalysts followed both E-R and L-H pathways, and the E-R played a dominant role in the reaction activity. PbCl 2 did not change the reaction pathways but made the reaction more difficult to happen. Finally, a possible mechanism model of Al 2 O 3 on PbCl 2 resistance over MC/AC catalyst was proposed. The addition of Al oxide effectivity increased the surface-active sites on the surface of AMC/AC catalyst. And the enhanced surface acidity and redox property served as the inherent chemical motivations for the anti-Pb poisoning ability of AMC/AC catalyst, leading to the difference in reactivity of the intermediates. On this basis, the reaction of PAMC/AC catalyst was stronger than that of PMC/AC catalyst in both E-R and L-H pathways. [Display omitted] [ABSTRACT FROM AUTHOR]

Lead salts poisoning was a great challenge for the catalysts application in selective catalytic reduction (SCR) reaction of NO x with NH 3 in stationary sources. Herein, several typical transition metal (Cu, Co and Zr) oxides modified Mn-Ce/AC catalysts were prepared by impregnation method, and the effects of Cu, Co and Zr doping on resistance PbCl 2 poisoning for the catalyst were investigated. The addition of three transition metal oxides improved the PbCl 2 resistance of Mn-Ce/AC catalyst and maintained excellent low-temperature denitrification activity of the catalyst. The lead resistance performance of the three metal oxides followed: Cu > Co > Zr oxides. The NO conversion of Cu-doping catalyst after PbCl 2 poisoning was only ca. 10% lower than that of fresh Mn-Ce/AC catalyst at 225 °C. Cu, Co and Zr doping could decrease the loss of specific surface area caused by poisoning, while Cu-doped catalyst showed lowest crystallinity of active components. Meanwhile, the contents of Mn4+ and chemisorbed oxygen in Cu-doped catalyst were higher than those in Co- or Zr-doped catalysts. Cu, Co and Zr doping improved the surface acidity and redox performance of the poisoned catalysts, with Cu-doped poisoned catalyst exhibiting nearly the same surface acidity and redox performance as the fresh Mn-Ce/AC catalyst. Furthermore, Cu doping could also improve NO adsorption and was in favor to the SCR process. Besides, in situ DRIFTS results showed that the catalytic reaction pathways of all the poisoned or modified catalysts were in accordance with both Langmuir-Hinshelwood (L-H) and Eley-Rideal (E-R) mechanisms. Finally, a possible anti-PbCl 2 poisoning mechanistic model of (Cu, Co and Zr) oxides modified on Mn-Ce/AC catalyst was proposed. [Display omitted] • Cu-modified MC/AC catalyst showed best resistance to PbCl 2 poisoning. • Transition metal oxides alleviated damage of PbCl 2 to MC/AC structure. • Redox ability and acidity of PbCl 2 -poisoned catalyst were promoted by modifying. • NH 3 -SCR reaction on PbCl 2 -poisoned catalyst followed L-H and E-R mechanism. [ABSTRACT FROM AUTHOR]

• Synergistic interaction of Sm and Fe enhanced Pb-resistance of Mn-Ce/AC catalyst. • Sm and Fe co-doping alleviated the damage of Pb species to catalyst structure. • Surface acidity and redox ability of Mn-Ce/AC catalyst were protected by Sm and Fe from lead. • NH 3 -SCR reaction on catalysts after Pb poisoning followed L-H and E-R mechanism. A novel anti-Pb poisoning Sm and Fe co-doped Mn-Ce/AC catalyst was prepared by impregnation method for low-temperature NH 3 -SCR of NO reaction. Maintaining the excellent low-temperature activity of Mn-Ce/AC catalyst, Sm and Fe co-doping remarkably enhanced the catalyst's Pb-resistance with NO conversion up to 77%. Sm and Fe co-doped poisoning-catalysts exhibited large specific surface area and pore volume, and the crystallinity of the MnO x and CeO x reduced. The redox properties and surface acidity of the lead poisoned SmFeMnCe/AC catalyst were effectively retained, which could promote NO oxidation and NH 3 activation, further benefiting the SCR reaction. In situ DRTFTS results indicated that the low-temperature NH 3 -SCR mechanism of all poisoned catalysts followed both L-H mechanism and E-R mechanism, and the L-H mechanism was dominated. On the one hand, the extraordinary lead resistance of Sm weakened the damage of lead species on the physicochemical properties of the catalyst; on the other hand, the high oxidation properties and surface acidity of Fe enhanced the catalytic activity of the poisoned catalyst. Finally, a possible synergistic mechanism model of Sm and Fe co-doping on Mn-Ce/AC catalyst against Pb-poisoning was proposed. [ABSTRACT FROM AUTHOR]

Zinc salts and SO 2 would cause Mn-Ce/AC catalyst poisoning, reducing the service life of the catalyst. In this study, the effects of Nb 2 O 5 on the tolerance of ZnCl 2 and SO 2 over Mn-Ce/AC catalyst were studied by the characterization results of BET, SEM, XRD, H 2 -TPR, NH 3 -TPD, TG and XPS. It indicated that doping Nb 2 O 5 could effectively enhance the SCR performance and N 2 selectivity of Zn-Mn-Ce/AC catalyst. Meanwhile, Nb 2 O 5 could significantly improve the SO 2 poisoning resistance of Zn-Mn-Ce/AC catalyst when sulfur dioxide was added into the reaction system. Nb 2 O 5 could react with SO 2 in a preferential way to restrain the sulfuration of manganese and cerium oxides on the catalyst. More importantly, Nb 2 O 5 reacted with SO 2 to form Nb sulfate and then formed a new acidic site on the Zn-Mn-Ce/AC catalyst surface, which promoted the adsorption of NH 3 and inhibited the adsorption of SO 2 , then restricted the reaction between NH 3 and SO 2 and hindered the formation of ammonium sulfate channels. [Display omitted] • Nb 2 O 5 could effectively improve the SCR activity of Zn-Mn-Ce/AC catalyst. • Nb 2 O 5 could effectively improve the N 2 selectivity of Zn-Mn-Ce/AC catalyst. • Nb 2 O 5 could improve anti-SO 2 poisoning performance of Zn-Mn-Ce/AC catalyst. • Nb 2 O 5 increased the redox ability, surface acidity, surface chemisorbed oxygen and Mn4+ content of Mn-Ce/AC catalyst. [ABSTRACT FROM AUTHOR]

• Toxicity effects of lead salt species on Mn-Ce/Cu-X catalyst were investigated. • Pb species might primarily occupy the active site of Mn and Cu species. • PbCl 2 and PbNO 3 species predominantly affected the Brønsted acid sites. • PbSO 4 and PbCO 3 species mainly impacted the adsorption of NO + O 2. For the sintering flue gas in steel industry, selective catalytic reduction (SCR) of NO x using NH 3 at low temperature in the presence of heavy metals is still a challenge. In this study, the toxicity effects of lead salt species (PbCl 2 , Pb(NO 3) 2 , PbSO 4 , PbCO 3) on Cu-exchanged zeolite X doped with Mn-Ce catalysts (MCCX) were investigated. All catalysts exhibited poor low-temperature SCR performance within 75–225 °C after Pb poisoning, and the poisoning effects of PbCl 2 , Pb(NO 3) 2 , PbSO 4 and PbCO 3 on MCCX catalyst varied. The PbSO 4 had the most serious poisoning on MCCX catalyst, while PbCO 3 had poisoning effect on catalysts even at 300 °C. Lead species poisoning had bad impact on the structure of zeolite X on MCCX catalyst, and caused some agglutination of Cu species. Likewise, the Pb species might primarily occupy the active site of Mn and Cu species and influence the redox property of catalysts, thereby obstructing the redox and oxidation cycles on catalysts surface. In addition, the PbCl 2 and PbNO 3 species predominantly affected the Brønsted acid sites and occupied the Cu or Mn active sites, inhabiting the absorption and conversion of nitrites and nitrates on the catalyst surface. Moreover, PbSO 4 and PbCO 3 species mainly impacted the adsorption of NO + O 2 and the conversion of nitrites and nitrates on the catalysts. [ABSTRACT FROM AUTHOR]

In this study, a series of K species or/and SO 2 poisoned Mn-Ce doped CuX (MCCX) catalysts were prepared from waste blast furnace slag (BFS), and the influence mechanism of K species or/and SO 2 poisoning on the catalysts in low-temperature NH 3 -SCR process was investigated. The results demonstrated that MCCX-KCl catalyst had poorer NO conversion than MCCX-K 2 O below 200 °C, and the co-existence of K species and SO 2 considerably inhibited NO conversion. Aggregation of the Cu active component might also be facilitated by co-poisoning with K species and SO 2. Furthermore, K species and SO 2 co-poisoned catalysts showed fewer isolated Cu2+ species and Mn4+ species than that of K-poisoned catalysts, indicating a decrease in active sites after the addition of SO 2. The co-effect of K 2 O/KCl and SO 2 species impaired the redox capacity and decreased the surface acidity than K-poisoned catalysts to a greater extent. Nevertheless, K-poisoning had little effect on the surface intermediates during SCR reaction process, and K-poisoned catalysts followed both Langmuir-Hinshelwood (L-H) and Eley-Rideal (E-R) mechanism. However, MCCX-KCl-SO 2 and MCCX-K 2 O-SO 2 catalysts contained fewer nitrate species, indicating that the co-effect of K species and SO 2 impeded the reaction between NO + O 2 species and pre-NH 3 species, thereby resulting in poor low-temperature NH 3 -SCR activity. [Display omitted] [ABSTRACT FROM AUTHOR]

The increase of solid wastes exerted great pressure on the environment and even damaged human health. Given this, the resource utilization of solid wastes became an inevitable trend of the industrial development. However, many researchers recognized that solid wastes with the component of Fe 2 O 3 , SiO 2 , Al 2 O 3 , TiO 2 , etc., could be utilized as the low-cost materials for preparing NH 3 -SCR catalysts, which could solve both the accumulation of solid wastes and the emission of NO x in industrial processes. Herein, some typical solid wastes, such as blast furnace slag (BFS), red mud (RM), coal fly ash (CFA), Fenton sludge (FS), etc., were extensively studied for their potential in NH 3 -SCR catalysts. Although the presence of some harmful components in solid wastes led to catalysts deactivation, they could still be excellent supports applied on NH 3 -SCR catalysts after proper pretreatment. In fact, these catalyst supports derived from solid wastes provided larger specific surface areas, thereby enhancing the NH 3 adsorption and redox capacity and facilitating the active ingredients loaded uniformly. Meanwhile, some useful impurities in solid wastes might also facilitate the NH 3 -SCR performance, achieving denitrification efficiency comparable to other catalysts made from costly materials. Moreover, most of these NH 3 -SCR catalysts performed significant SO 2 and/or H 2 O tolerance via metal oxides-doping, which would expand their potential for practical application in industry. Finally, the prospects for the application of solid wastes in NH 3 -SCR catalysts were also proposed. [Display omitted] • The preparation of SCR catalysts from solid wastes was reviewed. • The concept of treating waste gases with solid wastes was emphasized. • Mechanisms of removing NO x with solid waste catalysts were revealed. • The develop direction of solid waste catalysts was pointed out. [ABSTRACT FROM AUTHOR]

The study of SCR catalysts for nitrogen oxides reduction with NH 3 had recently attracted much attention. As a typical heavy metal element, Pb was prone to seriously damage the denitrification performance of SCR catalysts in flue-gas environment. This work systematically reviewed the mechanisms of Pb poisoning and anti-deactivation measures reported these years for SCR catalysts. The mechanisms of Pb poisoning were summarized from both physical and chemical aspects, including the specific surface area, redox ability and surface acidity of the catalysts, and the corresponding reaction paths of the catalysts were also considered during the SCR process. In the meantime, this paper reviewed the anti-deactivation mechanisms and measures currently used to solve the problem of lead poisoning for SCR catalysts. The main methods included adding active substances to improve the redox ability and surface acidity of the catalysts, using ions or anti-poisoning sites to preferentially bind to Pb species, or using the structural characteristics of the carriers to prevent Pb from contacting with active substances. The concrete measures included the modification of catalysts with metal oxides and solid super acids, the change of carriers' structure, and the dual effect of carriers and active materials. Finally, a prospect of lead poisoning for further research on SCR catalysts was proposed. [Display omitted] • Physical and chemical mechanisms of Pb poisoning on SCR catalyst were reviewed. • Anti-inactivation mechanisms for SCR catalyst in the presence of Pb were clarified. • Recent advances in anti-Pb measures of SCR catalysts were summarized. • Challenges for Pb poisoning catalyst in industrial application were proposed. [ABSTRACT FROM AUTHOR]

In this study, CuX zeolite supported Mn and/or Ce oxides catalysts were synthesized by combining ion exchange and impregnation methods, and the zeolite X was generated using blast furnace slag (BFS). Doping Mn-Ce oxides onto the CuX catalyst, which has excellent resistance to SO 2 +H 2 O, improved the catalyst's activity for NH 3 -SCR at lower temperature. In addition, electron transfer from Mn4+ to Ce3+ and Cu2+ was enhanced, and the concentration of isolated Cu2+ and chemisorbed oxygen species was higher in the Mn-Ce/CuX catalyst. Also, the Mn-Ce/CuX catalyst provided excellent SCR activity because of its high acid capacity, which allowed it to provide extra acid sites, and its high redox ability, which enhanced the re-oxidized and re-reduced cycles. Additionally, produced sulfates on the catalyst surface after SO 2 and H 2 O poisoning might occupy Cu2+ active sites and affect the SCR process by competing with acid sites, nitrate species and intermediates on the Mn-Ce/CuX catalyst. [Display omitted] • Mn or Ce/CuX catalysts were prepared successfully from blast furnace slag. • Effects of Cu sites and Mn-Ce addition on the properties of the catalyst were analyzed. • Relationship between the physicochemical properties and catalytic activities of the catalysts was revealed. • Mn-Ce/CuX catalyst had excellent low-temperature NH 3 -SCR activity and SO 2 or H 2 O resistance. [ABSTRACT FROM AUTHOR]