Citation: Ganchang Lei, Yong Zheng, Yanning Cao, Lijuan Shen, Shiping Wang, Shijing Liang, Yingying Zhan, Lilong Jiang. Deactivation Mechanism of COS Hydrolysis over Potassium Modified Alumina[J]. Acta Physico-Chimica Sinica, ;2023, 39(9): 221003. doi: 10.3866/PKU.WHXB202210038 shu

Deactivation Mechanism of COS Hydrolysis over Potassium Modified Alumina

Ganchang Lei ^{1, 2} ,
Yong Zheng ^{1, 2} ,
Yanning Cao ^{1, 2} ,
Lijuan Shen ^{1, 3,,} ,
Shiping Wang ^{1, 2} ,
Shijing Liang ^{1, 2} ,
Yingying Zhan ^{1, 2,,} ,
Lilong Jiang ^{1, 2,,}

1.
National Engineering Research Center of Chemical Fertilizer Catalyst, School of Chemical Engineering, Fuzhou University, Fuzhou 350002, China
2.
China Fujian Innovation Laboratory of Chemical Engineering, Qingyuan Innovation Laboratory, Quanzhou 302801, Fujian Province, China
3.
College of Environmental Science and Engineering, College of Carbon Neutral Modern Industry, Fujian Key Laboratory of Pollution Control & Resource Reuse, Fujian Normal University, Fuzhou 350007, China

Corresponding author: Lijuan Shen, syhgslj@fzu.edu.cn Yingying Zhan, zhanyingying@fzu.edu.cn Lilong Jiang, jll@fzu.edu.cn
Received Date: 27 October 2022
Revised Date: 9 November 2022
Accepted Date: 11 November 2022
Available Online: 16 November 2022
Fund Project: the National Natural Science Foundation of China 21825801the National Natural Science Foundation of China 22208053the National Natural Science Foundation of China 22178057the National Natural Science Foundation of China 21878053the National Natural Science Foundation of China 22278073the National Natural Science Foundation of China 22208055the National Natural Science Foundation of China 22078063the Natural Science Foundation of Fujian Province 2020H6007the Natural Science Foundation of Fujian Province 2022J05131

Carbonyl sulfide (COS) is commonly found in conventional fossil fuels, such as nature gas, oil-associated gas, and blast-furnace gas, and its untreated emission not only corrodes pipelines and poisons catalysts but will also inevitably pollute the environment and endanger human health. Catalytic hydrolysis is recognized as the most promising strategy to eliminate COS because it can be performed under mild reaction conditions with a high removal efficiency. Notably, alkali metals promote catalytic COS hydrolysis over Al₂O₃ owing to their electron donor properties, basicity, and electrostatic adsorption. However, despite the significant attraction of using potassium-promoted Al₂O₃ (K₂CO₃/Al₂O₃) as conventional catalysts for COS hydrolysis, the mechanism of COS hydrolysis over K₂CO₃/Al₂O₃ remains unclear and is controversial owing to the complex composition of the K species. In this study, commercial Al₂O₃ modified with potassium and sodium salts were synthesized using the wet impregnation method and characterized by various techniques. Based on the results of the activity measurements, the K₂CO₃-, K₂C₂O₄-, NaHCO₃-, Na₂CO₃-, and NaC₂O₄-modified catalysts had a positive effect on COS hydrolysis. Among them, the K₂CO₃/Al₂O₃ catalyst exhibited the highest COS conversion. Notably, the K₂CO₃/Al₂O₃ catalyst exhibited an excellent catalytic performance (~93%, 20 h), which is significantly better than that of pristine Al₂O₃ (~58%). Furthermore, this study provides strong evidence for the role of H₂O during catalytic hydrolysis over K₂CO₃/Al₂O₃ using in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and X-ray photoelectron spectroscopy (XPS). The in situ DRIFTS analysis revealed that hydrogen thiocarbonate formed as an intermediate during COS hydrolysis over K₂CO₃/Al₂O₃. Meanwhile, the XPS findings suggested that sulfates and elemental sulfur accumulated on the catalyst surface, which may have contributed to catalyst poisoning. Additionally, the effect of water vapor content in the reaction pathway of COS hydrolysis over K₂CO₃/Al₂O₃ was investigated. The presence of excess water resulted in a reduction in catalytic activity owing to competitive adsorption between H₂O and COS molecules on the catalyst surface. The enhancement in the catalytic activity over K₂CO₃/Al₂O₃ may be attributed to the formation of HO-Al-O-K interfacial sites. More importantly, all the catalysts were used under industrially relevant conditions, which provides valuable theoretical guidance for practical applications in the future. Thus, this detailed mechanistic study reveals new insights into the roles of the interfacial K co-catalyst, which provides a new opportunity for the rational design of stable and efficient catalysts for COS hydrolysis.
- Carbonyl sulfide,
- Catalytic hydrolysis,
- HO-Al-O-K interface site,
- Deactivation mechanism,
- Industrial-relevant condition
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