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An investigation on the promoting effect of Pr modification on SO2 resistance over MnOx catalysts for selective reduction of NO with NH3

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Abstract

Pr-modified MnOx catalyst was synthesized through a facile co-precipitation process, and the results showed that MnPrOx catalyst exhibited much better selective catalytic reduction (SCR) activity and SO2 resistance performance than pristine MnOx catalyst. The addition of Pr in MnOx catalyst led to a complete NO conversion efficiency in 120–220 °C. Moreover, Pr-modified MnOx catalyst exhibited a superior resistance to H2O and SO2 compared with MnOx catalyst. After exposing to SO2 and H2O for 4 h, the NO conversion efficiency of MnPrOx catalyst could remain to 87.6%. The characterization techniques of XRD, BET, hydrogen-temperature programmed reduction (H2-TPR), ammonia-temperature programmed desorption (NH3-TPD), XPS, TG and in situ diffuse reflectance infrared spectroscopy (DRIFTS) were adopted to further explore the promoting effect of Pr doping in MnOx catalyst on SO2 resistance performance. The results showed that MnPrOx catalyst had larger specific surface area, stronger reducibility, and more L acid sites compared with MnOx catalyst. The relative percentage of Mn4+/Mnn+ on the MnPrOx-S catalyst surface was also much higher than those of MnOx catalyst. Importantly, when SO2 exists in feed gas, PrOx species in MnPrOx catalyst would preferentially react with SO2, thus protecting the Mn active sites. In addition, the introduction of Pr might promote the reaction between SO2 and NH3 rather than between SO2 and Mn active sites, which was also conductive to protect the Mn active sites to a great extent. Since the presence of SO2 in feed gas had little effect on NH3 adsorption on the MnPrOx catalyst surface, and the inhibiting effect of SO2 on NO adsorption was alleviated, SCR reactions could still proceed in a near-normal way through the Eley-Rideal (E-R) mechanism on Pr-modified MnOx catalyst, while SCR reactions through the Langmuir-Hinshelwood (L-H) mechanism were suppressed slightly.

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Funding

This work was supported by the National Natural Science Foundation of China (51779024 and 51979045), the Natural Science Foundation of Liaoning Province of China (2020MS130), and the Fundamental Research Funds for the Central Universities (3132019330).

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Authors and Affiliations

  1. Marine Engineering College, Dalian Maritime University, No.1, Linghai Road, Dalian, 116026, China

    Guangpeng Zhai, Zhitao Han, Huan Du, Yu Gao & Xinxiang Pan

  2. Liaoning Research, Center for Marine Internal Combustion Engine Energy-Saving, Dalian, 116026, China

    Zhitao Han & Xinxiang Pan

  3. Guangdong Ocean University, Zhanjiang, 524088, Guangdong, China

    Xinxiang Pan

Authors
  1. Guangpeng Zhai
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  2. Zhitao Han
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  3. Huan Du
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  4. Yu Gao
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  5. Xinxiang Pan
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Contributions

ZH: Design experiments, revise manuscript. GZ: Conduct experiments, process data, write manuscript. HD: Analyze data. YG: Draw pictures. XP: Revise manuscript.

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Correspondence to Zhitao Han or Xinxiang Pan.

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Highlights

• Pr-modified MnOx catalyst exhibited superior SO2 resistance over MnOx catalyst.

• Pr modification was beneficial to inhibit the sulfation of Mn active sites.

• The presence of SO2 imposed little impact on NH3 adsorption on Lewis acid sites of MnPrOx catalyst while exerted some negative effects on NO adsorption.

• SCR reactions for MnPrOx catalyst could still proceed through both E-R and L-H mechanisms in the presence of SO2.

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Zhai, G., Han, Z., Du, H. et al. An investigation on the promoting effect of Pr modification on SO2 resistance over MnOx catalysts for selective reduction of NO with NH3. Environ Sci Pollut Res 29, 17295–17308 (2022). https://doi.org/10.1007/s11356-021-17006-3

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