Precise regulation of acid pretreatment for red mud SCR catalyst: Targeting on optimizing the acidity and reducibility

doi:10.1007/s11783-021-1447-x

Front. Environ. Sci. Eng.

2022, Vol. 16

Issue (7) : 88 https://doi.org/10.1007/s11783-021-1447-x

RESEARCH ARTICLE

Precise regulation of acid pretreatment for red mud SCR catalyst: Targeting on optimizing the acidity and reducibility

Xiang Zhang¹, Yue Xuan¹, Bin Wang¹, Chuan Gao¹, Shengli Niu¹, Gaiju Zhao⁴, Dong Wang^1,²(

), Junhua Li³, Chunmei Lu¹, John C. Crittenden²

¹. National Engineering Laboratory for Coal-Burning Pollutants Emission Reduction, School of Energy and Power Engineering, Shandong University, Jinan 250061, China
². School of Civil and Environmental Engineering and the Brook Byers Institute for Sustainable Systems, Georgia Institute of Technology, Atlanta, GA 30332, USA
³. State Key Joint Laboratory of Environment Simulation and Pollution Control, National Engineering Laboratory for Multi Flue Gas Pollution Control Technology and Equipment, School of Environment, Tsinghua University, Beijing 100084, China
⁴. Energy Institute, Qilu University of Technology (Shandong Academy of Sciences), Jinan 250013, China

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Abstract

• The optimum SCR activity was realized by tuning the acid pretreatment.

• Optimized catalysts showed NO_x conversion above 90%.

• The NH₃ and NO adsorption capacity of Al-O₃-Fe is stronger than Fe-O₃-Fe.

• The formation of almandine consumes Fe³⁺ and Al³⁺ and weakens their interaction.

Red mud (RM), as an alkaline waste, was recently proved to be a promising substitute for the SCR catalyst. Dealkalization could improve the acidity and reducibility of red mud, which were critical for SCR reaction. However, the dealkalization effect depended on the reaction between acid solution and red mud. In this study, we realized the directional control of the chemical state of active sites through tuning the acid pretreatment (dealkalization) process. The pretreatment endpoint was controlled at pH values of 3–5 with diluted nitric acid. When the pH values of red mud were 3 and 5 (CRM-3 and CRM-5), activated catalysts showed NO_x conversion above 90% at 275°C–475°C. The high initial reaction rate, Ce³⁺/(Ce³⁺ + Ce⁴⁺) ratio, and surface acidity accounted for the excellent SCR performance of CRM-5 catalyst. Meanwhile, more Fe³⁺ on the CRM-3 surface improved the NH₃ adsorption. There was a strong interaction between Al and Fe in both CRM-5 and CRM-3 catalysts. DFT results showed that the adsorption capacity of the Al-O₃-Fe for NH₃ and NO is stronger than that of Fe-O₃-Fe, which enhanced the NO_x conversion of the catalyst. However, the almandine was formed in CRM-4, consumed part of Fe³⁺ and Al³⁺, and the interaction between Al and Fe was weakened. Also, deposited almandine on the catalyst surface covered the active sites, thus leading to lower NH₃-SCR activity.

Keywords Air pollution control Nitrogen oxides Selective catalytic reduction Red mud Solid waste utilization

Corresponding Author(s): Dong Wang

Issue Date: 23 November 2021

Cite this article:

Xiang Zhang,Yue Xuan,Bin Wang, et al. Precise regulation of acid pretreatment for red mud SCR catalyst: Targeting on optimizing the acidity and reducibility[J]. Front. Environ. Sci. Eng., 2022, 16(7): 88.

URL:

https://academic.hep.com.cn/fese/EN/10.1007/s11783-021-1447-x
https://academic.hep.com.cn/fese/EN/Y2022/V16/I7/88

Fig.1 (a), (b) The α-Fe₂O₃ (001) model (while the M is purple, it is Al-Fe₂O₃ (001)). The iron atoms are gray, the aluminum atoms are purple, and the oxygen atoms are red. (c) Schematic diagram of catalysts preparation. (d) The catalysts De-NO_x efficiency. (e) Reaction rate per specific surface area calculated at 225°C. Reaction conditions: [NH₃] = [NO] = 0.05%, [O₂] = 4%, and balanced N₂, total ﬂow= 2000 mL/min, gas hourly space velocity (GHSV) = 30000/h.

Fig.2 (a), (b) XRD spectra, and (c), (d) element composition of the supernatant of the acid-leached sample detected by ICP-OES experiments.

Tab.1 Different crystallite parameters of CRM-A catalysts by XRD results

Tab.2 Surface physical properties of the CRM-A catalysts by BET results

Fig.3 XPS spectra of the CRM-5, CRM-4, and CRM-3 catalysts over the spectral regions of (a) Fe 2p, (b) Ce 3d, and (c) O 1s.

Tab.3 Surface chemical properties of the CRM-A catalysts by XPS results

Fig.4 (a) NH₃-TPD profiles of the CRM-5, CRM-4, and CRM-3 catalysts, (b) H₂-TPR profiles of the catalysts, and (c) H₂ consumption.

Fig.5 (a) H₂O and SO₂ effect on NO_x conversion over the CRM-5 catalyst, (b) FT-IR spectra of fresh and poisoned CRM-5 catalyst.

Fig.6 Optimized adsorption model of the NO on (a) α-Fe₂O₃(001), (b) and (c) Al-Fe₂O₃ (001) surfaces; optimized adsorption model of the NH₃ on (d) α-Fe₂O₃ (001), (e) and (f) Al-Fe₂O₃ (001) surfaces. The iron atoms are gray, the aluminum atoms are purple, the oxygen atoms are red, and the hydrogen atoms are white.

Tab.4 The optimal distance and E_ad for models to adsorb NO and NH₃

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