The problems of easily inactivated by SO 2 poisoning and high N 2 O formation for MnO x based catalysts hinder its application in selective catalytic reduction (SCR) of NO x with NH 3 . The SO 2 poisoning mechanism has been well demonstrated, but the N 2 O formation mechanism was still controversial due to previous limited study. Herein, MnO 2 supported on MO x (Mn/M, M = Al, Si and Ti) were prepared by wet impregnation method to investigate the carrier effect on the formation of N 2 O. Although all of selected supports had a large amount of surface acid sites, only forming strong active-support interaction can separate the activation sites of NH 3 and NO + O 2 . Accordingly, the activation of NH 3 and NO + O 2 on MnTi was respectively occurred on TiO 2 and MnO 2 , but both NH 3 and NO + O 2 was activated on MnO 2 over MnAl and MnSi samples. The over-activation (NH 2 dissociated into NH) of NH 3 would be effectively inhibited when NH 3 activation was occurred on TiO 2 , thus it can significantly suppress the formation of N 2 O. In contrast, the NH 3 species would sharply decompose into NH on MnO 2 and then lead to the high amount of N 2 O. Finally, we proposed some methods that might effectively improve the selectivity of MnO x- based catalysts.
Yangfan Chen,Hongyan Yan,Wenxin Teng,Jiangling Li,Weizao Liu,Shan Ren,Jian Yang,Qingcai Liu
NH 3 -SCR technology with commercialized V 2 O 5 -WO 3 (MoO 3 )/TiO 2 catalysts has become the most efficient technology for the removal of NO x from coal-fired power plants. However, the weaknesses of V 2 O 5 -WO 3 (MoO 3 )/TiO 2 catalysts such as the biotoxicity of vanadium species and high cost restrict their increased applicability. Fe 2 O 3 -based NH 3 -SCR catalysts show potential in placing traditional catalysts due to their good N 2 selectivity, excellent environmentally friendly performance, high thermal stability, and low cost. In this work, low cost Fe 2 O 3 -containing solid waste was exploited as the base material for NH 3 -SCR catalyst preparing. Moreover, bulk MoO 3 and MoO 3-x nanosheets decorated Fe 2 O 3 composite NH 3 -SCR catalysts were synthesized and both revealed conspicuously improved NO x removal efficiency compared with bare-Fe 2 O 3 catalyst. However, the N 2 selectivity of these two catalysts showed significant differences. Therefore, comprehensive characterizations, NH 3 oxidation experiments, and in-situ diffusion Fourier transform infrared spectroscopy (DRIFTS) experiments were performed to determine the N 2 O formation pathways of the above two catalysts. The redox properties were highly related to the N 2 O generated from NH 3 oxidation. Moreover, the huge difference in NH 3 and NO adsorption ability led to disparate reaction mechanisms over the two catalysts. This new understanding of the N 2 O formation mechanism has the potential to guide the rational design of improved NH 3 -SCR catalysts suffering from low N 2 selectivity.
High N 2 O selectivity of MnO x -TiO 2 catalyst hinders its development in ammonia selective catalytic reduction (NH 3 -SCR) of NO x . Herein, a series of MnO x -TiO 2 catalyst with different Mn/Ti ratio were prepared by wet-impregnation method to study the N 2 O formation during ammonia selective catalytic reduction (NH 3 -SCR) of NO x from the perspective of catalyst. It is found that MnO x and TiO 2 species are the mainly redox and acid sites for the NH 3 -SCR denitration reaction over MnO x -TiO 2 catalyst, respectively. As the Mn/Ti ratio increases, MnO x species layer expanded on TiO 2 support, leading to increase of redox sites but decrease of surface acid sites. These changes contribute to the occurrence of the no-selective oxidation of NH 3 on MnO x species and the over-activation of NH 3 at Mn-Ti interface, resulting in the formation of N 2 O via the route of 2NH 3 + 2O 2 → N 2 O + 3H 2 O and 4NO + 4NH 3 + 3O 2 → 4N 2 O + 6H 2 O, respectively. Through this work, it can be speculated that both improving MnO x dispersion and increasing surface acidity of catalyst are feasible strategy for suppressing the N 2 O formation on MnO x -TiO 2 .
The CeO 2 -TiO 2 (CeTi) and CeO 2 /WO 3 -TiO 2 (CeWTi) catalysts were prepared by a sol-gel precipitation method and their NH 3 -NO/NO 2 selective catalytic reduction (SCR) performance was studied. N 2 O formation and effect of oxygen concentration on SCR performance over CeWTi catalyst were also investigated while varying the NO 2 /NO x ratio. Results indicate that fast SCR behavior of CeWTi catalyst has the best NH 3 -NO/NO 2 SCR performance due to the catalyst reoxidation rate by NO 2 higher than by O 2 . Compared with CeTi catalyst, CeWTi catalyst exhibits higher de-NO x performance under NH 3 -NO/NO 2 SCR conditions. As the CeTi and CeWTi catalysts exhibit similar redox property, addition of WO 3 provides more acid sites which accelerate the reaction between NH 4 NO 3 and NO to get a superior low-temperature activity. Amount of N 2 O formation shows a peak at 250 °C mainly derived from NH 4 NO 3 decomposition.
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