DEACTIVATION MECHANISM OF γ-Al<sub>2</sub>O<sub>3</sub> BASED CATALYSTS FOR THE CATALYTIC HYDROLYSIS OF CARBONYL SULFIDE IN PRESENCE OF HCl

CAO Qiang; LI Yuran; WANG Bin; WANG Jiancheng; ZHU Tingyu

doi:10.13205/j.hjgc.202312022

Volume 41 Issue 12

Dec. 2023

Turn off MathJax

Article Contents

Article Navigation > ENVIRONMENTAL ENGINEERING > 2023 > 41(12): 182-189

CAO Qiang, LI Yuran, WANG Bin, WANG Jiancheng, ZHU Tingyu. DEACTIVATION MECHANISM OF γ-Al2O3 BASED CATALYSTS FOR THE CATALYTIC HYDROLYSIS OF CARBONYL SULFIDE IN PRESENCE OF HCl[J]. ENVIRONMENTAL ENGINEERING , 2023, 41(12): 182-189. doi: 10.13205/j.hjgc.202312022

Citation:

CAO Qiang, LI Yuran, WANG Bin, WANG Jiancheng, ZHU Tingyu. DEACTIVATION MECHANISM OF γ-Al₂O₃ BASED CATALYSTS FOR THE CATALYTIC HYDROLYSIS OF CARBONYL SULFIDE IN PRESENCE OF HCl[J]. ENVIRONMENTAL ENGINEERING , 2023, 41(12): 182-189. doi: 10.13205/j.hjgc.202312022

Citation:

PDF( 11224 KB)

DEACTIVATION MECHANISM OF γ-Al₂O₃ BASED CATALYSTS FOR THE CATALYTIC HYDROLYSIS OF CARBONYL SULFIDE IN PRESENCE OF HCl

doi: 10.13205/j.hjgc.202312022

1. State Key Laboratory of Clean and Efficient Coal Utilization, Taiyuan University of Technology, Taiyuan 030024, China;
2. Innovation Academy for Green Manufacturing, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China

Received Date: 2023-03-28
Available Online: 2024-03-08

Abstract

Abstract

With the implementation of ultra-low emissions in the iron and steel industry, applying blast furnace gas desulfurization technology is very urgent. The sulfur-containing component in blast furnace gas mainly is carbonyl sulfide (COS), and the catalytic hydrolysis method on the γ-Al₂O₃-based catalyst is usually selected to generate H₂S and then further removed. However, the hydrolysis catalyst is easily deactivated in the presence of HCl from the blast furnace gas. In this work, the γ-Al₂O₃-based catalyst was prepared by the impregnation method supported with alkali metals, Na or K, as an active component. The effect of HCl on the hydrolysis activity and deactivation mechanism of the catalyst was investigated through the combined platform of a fixed-bed reactor and gas chromatography. The hydrolysis efficiency of COS was tested at 120 ℃, gas hourly space velocity (GHSV) of 150000 h^-1. The results showed that hydrolysis efficiency and chlorine resistance on catalysts Na/Al₂O₃ and K/Al₂O₃ were higher than that on γ-Al₂O₃, and the chlorine resistance on Na/Al₂O₃ was higher than that on K/Al₂O₃. The active components, Na and K increased the content of alkaline centers of the catalyst, promoted the COS hydrolysis reaction and improved the catalyst activity. The active component Na or K preferentially reacts with HCl to form metal chloride, weakens the chlorination effect of HCl on the support components and improves the chlorine resistance of the catalyst. The deactivation mechanism of Na/Al₂O₃ and K/Al₂O₃ catalysts in the presence of HCl was investigated. HCl occupied the medium-strong alkaline center (M—O) of the catalysts and reacted with the active components of alkali metals to form metal chloride (M—Cl), and then reduced the catalyst activity. The loss of Na in Na/Al₂O₃ in the presence of HCl was significantly lower than K in K/Al₂O₃, which improved the chlorine resistance of Na/Al₂O₃ catalyst.
- blast furnace gas desulfurization,
- catalytic hydrolysis,
- carbonyl sulfide,
- aluminum-based catalyst,
- alkali metals,
- hydrogen chloride

FullText(HTML)

References(20)

References

[1]	World Steel in Figures 2023[EB/OL] https://worldsteel.org/steel-topics/statistics/world-steel-in-figures-2023/.
[2]	郭玉华.高炉煤气净化提质利用技术现状及未来发展趋势[J].钢铁研究学报, 2020, 32(7): 525-531.
[3]	王斌,林玉婷,李玉然,等.高炉煤气羰基硫催化水解过程影响因素[J].洁净煤技术, 2021, 27(5): 233-238.
[4]	CAO R, NING P, WANG X Q, et al. Low-temperature hydrolysis of carbonyl sulfide in blast furnace gas using Al₂O₃-based catalysts with high oxidation resistance[J]. Fuel, 2021,310: 122295.
[5]	刘艳敏,辛渊,李保良,等.氯元素对高炉煤气管道的腐蚀与预防[J].天津冶金,2022(5):8-10,14.
[6]	程正霖,朱晓华,李鹏飞.高炉生产过程中氯的来源、迁移转化及影响[J].环境工程,2021,39(4):86-91.
[7]	李雯博,史连军,王梦,等.合成气制甲醇CuZnAl催化剂失活因素研究[J].天然气化工(C1化学与化工),2020,45(5):31-38.
[8]	李春虎,郭汉贤,谈世韶.碱改性γ-Al₂O₃催化剂表面碱强度分布与COS水解活性的研究[J].分子催化,1994(4):305-312.
[9]	YAO X J, GAO F, DONG L. The application of incorporation model in γ-Al₂O₃ supported single and dual metal oxide catalysts: a review[J]. Chin J Catal, 2013,34: 1975-1985.
[10]	LI C M, ZHAO S Y, YAO X L, et al. The catalytic mechanism of intercalated chlorine anions as active basic sites in MgAl-layered double hydroxide for carbonyl sulfide hydrolysis[J]. Environmental Science and Pollution Research, 2022, 29(7):10605-10616.
[11]	CHANG F Y, CHEN J C, WEY M Y. Effects of oxygen and hydrogen chloride on NO removal efficiency by Rh/Al₂O₃ and Rh-Na/Al₂O₃ catalysts[J]. Applied Catalysis A: General, 2009, 359(1/2): 88-95.
[12]	ZHAO S Z, YI H H, TANG X L, et al. Calcined ZnNiAl hydrotalcite-like compounds as bifunctional catalysts for carbonyl sulfide removal[J]. Catalysis Today, 2019, 327: 161-167.
[13]	YI H H, ZHAO S Z, TANG X L, et al. Influence of calcination temperature on the hydrolysis of carbonyl sulfide over hydrotalcite-derived Zn-Ni-Al catalyst[J]. Catalysis Communications, 2011, 12(15): 1492-1495.
[14]	ZHAO S Z, YI H H, TANG X L, et al. Low temperature hydrolysis of carbonyl sulfide using Zn-Al hydrotalcite-derived catalysts[J]. Chemical Engineering Journal, 2013, 226: 161-165.
[15]	KIM S, GUPTA N K, BAE J, et al. Fabrication of coral-like Mn₂O₃/Fe₂O₃ nanocomposite or room temperature removal of hydrogen sulfide[J]. Journal of Environmental Chemical Engineering, 2021, 9(3): 105216.
[16]	GUPTA N K, BAE J, KIM K S. Metal organic framework derived NaCo_xO_y for room temperature hydrogen sulfide removal[J]. Scientific Reports, 2021, 11(1): 14740.
[17]	MENG W, WANG X, DAI Q, et al. Catalytic combustion of chlorobenzene over Mn-Ce/Al₂O₃ catalyst promoted by Mg[J]. Catalysis Communications, 2010, 11(12):1022-1025.
[18]	WANG Q, LIN F, ZHOU J, et al. Effect of HCl and o-DCBz on NH₃-SCR of NO over MnO_x/TiO₂ and MnO_x-CeO₂/TiO₂ catalysts[J]. Applied Catalysis A: General, 2020, 605: 117801.
[19]	LIN F, WANG Q L, HUANG X L, et al. Investigation of chlorine-poisoning mechanism of MnO_x/TiO₂ and MnO_x-CeO₂/TiO₂ catalysts during o-DCBz catalytic decomposition: experiment and first-principles calculation[J]. Journal of Environmental Management,2021: 298.
[20]	李凯. COS、CS₂水解催化剂的开发及机理研究[D].昆明:昆明理工大学,2013.