Tailoring the simultaneous abatement of methanol and NO<sub><i>x</i></sub> on Sb-Ce-Zr catalysts via copper modification

doi:10.1007/s11684-022-1565-0

Front. Environ. Sci. Eng.

2022, Vol. 16

Issue (10) : 130 https://doi.org/10.1007/s11684-022-1565-0

RESEARCH ARTICLE

Tailoring the simultaneous abatement of methanol and NO_x on Sb-Ce-Zr catalysts via copper modification

Xiaoqiang Wang^1,², Yanye Zhu¹, Yue Liu¹(

), Xiaole Weng¹, Zhongbiao Wu¹

¹. Department of Environmental Engineering, Zhejiang University, Hangzhou 310058, China
². College of Biological, Chemical Science and Engineering, Jiaxing University, Jiaxing 314001, China

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Abstract

● Cu addition enhances CH₃OH oxidation and alleviates its inhibitory effect on SCR.

● Cu addition improves the activation of SCR reactants in the presence of methanol.

● Damaged structure by more Cu addition decreases specific surface area and acidity.

● Excessive Cu addition would lead to the narrowing of SCR temperature window.

Simultaneously removal of NO_x and VOCs over NH₃-SCR catalysts have attracted lots of attention recently. However, the presence of VOCs would have negative effect on deNO_x efficiency especially at low temperature. In this study, copper modification onto Sb_0.5CeZr₂O_x (SCZ) catalyst were performed to enhance the catalytic performance for simultaneous control of NO_x and methanol. It was obtained that copper addition could improve the low-temperature activity of both NO_x conversion and methanol oxidation, where the optimal catalyst (Cu_0.05SCZ) exhibited a deNO_x activity of 96% and a mineralization rate of 97% at 250 °C, which are around 10% higher than that of Cu free sample. The characterization results showed that copper addition could obviously enhance the redox capacity of the catalysts. As such, the inhibition effect of methanol incomplete oxidation on NO adsorption and NH₃ activation were then lessened and the conversion of surface formamide species were also accelerated, resulting in the rising of NO_x conversion at low temperature. However, excessive copper addition would damage the Sb-Ce-Zr oxides solid solution structure owing to Cu-Ce strong interactions, decreasing the surface area and acidity. Meanwhile, due to easier over-oxidation of NH₃ with more Cu addition, the temperature window for NO_x conversion would become quite narrow. These findings could provide useful guidelines for the synergistic removal of VOCs over SCR catalyst in real application.

Keywords Copper modification Sb-CeZr₂O_x catalyst NO_x Methanol Simultaneous removal

Corresponding Author(s): Yue Liu

Issue Date: 31 March 2022

Cite this article:

Xiaoqiang Wang,Yanye Zhu,Yue Liu, et al. Tailoring the simultaneous abatement of methanol and NO_x on Sb-Ce-Zr catalysts via copper modification[J]. Front. Environ. Sci. Eng., 2022, 16(10): 130.

URL:

https://academic.hep.com.cn/fese/EN/10.1007/s11684-022-1565-0
https://academic.hep.com.cn/fese/EN/Y2022/V16/I10/130

Fig.1 The simultaneous catalytic abatement performance of methanol and NO_x over Cu_xSCZ catalysts: (a) deNO_x activity, (b) N₂ selectivity, (c) CH₃OH conversion, and (d) CO₂ yield. Reaction conditions: [NO] = [NH₃] = 0.06%, [CH₃OH] = 0.12%, [O₂] = 5 vol.%, [H₂O] = 5 vol.%, N₂ balance, GHSV = 100, 000 h^?1.

Tab.1 Physical information and calculated XPS results of Cu_xSCZ catalysts

Fig.2 XRD patterns (a) and Raman spectra (λ = 532 nm) (b) of the Cu_xSCZ samples.

Fig.3 HRTEM images for (a, b) SCZ, (c, d) Cu_0.05SCZ, and (e, f) Cu_0.1SCZ samples.

Fig.4 XPS spectra of (a) Ce 3d, (b) O 1s, and (c) Cu 2p3/2 in the Cu_xSCZ samples.

Fig.5 NH₃-TPD (a) and H₂-TPR (b) profiles of the Cu_xSCZ catalysts.

Fig.6 The mass signal of NO-TPD experiment: (a) NO and (b) NO₂; (c) DRIFT spectra of NO + O₂ on catalysts pretreated with methanol; (d) Evolution of NO₂ during NO oxidation over SCZ and Cu_0.05SCZ samples.

Fig.7 The influence of methanol on (a) NH₃-TPD, (b) NH₃-IR and NH₃ oxidation results: (c) NH₃ conversion and (d) evolution of NO_x of SCZ and Cu_0.05SCZ samples.

Fig.8 DRIFT spectra of E-R reaction pathway on the Cu_0.05SCZ sample: (a) pretreated with methanol/He; (b) pretreated with He.

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