γ-Al<sub>2</sub>O<sub>3</sub>基COS水解催化剂在含HCl气氛的失活机理

曹强; 李玉然; 王斌; 王建成; 朱廷钰

doi:10.13205/j.hjgc.202312022

γ-Al₂O₃基COS水解催化剂在含HCl气氛的失活机理

doi: 10.13205/j.hjgc.202312022

曹强^1,2,
李玉然^2,,
王斌²,
王建成^1,,
朱廷钰^1,2

1. 太原理工大学省部共建煤基能源清洁高效利用国家重点实验室, 太原 030024;
2. 中国科学院过程工程研究所中国科学院绿色过程制造创新研究院, 北京 100190

基金项目:

河北省重点研发计划项目(21373702D)

河钢集团重点科技项目(HG2021117)

详细信息

作者简介:
曹强(1996-),男,硕士研究生,主要研究方向为高炉煤气脱硫。caoqiang@ipe.ac.cn

通讯作者:
李玉然。yrli@ipe.ac.cn

王建成。wangjiancheng@tyut.edu.cn

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- 被引次数: 0
出版历程
- 收稿日期: 2023-03-28
- 网络出版日期: 2024-03-08

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

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

摘要

摘要: 随着钢铁行业超低排放的推进,实施高炉煤气脱硫迫在眉睫。高炉煤气中含硫组分主要为羰基硫(COS),常采用γ-Al₂O₃基催化剂将COS催化水解为H₂S再进一步脱除,但是煤气中的HCl组分容易导致催化剂失活。采用浸渍法在γ-Al₂O₃上负载碱金属Na、K制备铝基水解催化剂,在固定床-气相色谱联用装置上,考察水解催化剂在含HCl气氛的失活机理。在120 ℃、150000 h^-1空速条件下测试COS的水解效率。结果表明:Na/Al₂O₃和K/Al₂O₃催化剂的活性及抗氯性能均高于γ-Al₂O₃,且Na/Al₂O₃的抗氯性高于K/Al₂O₃。活性组分Na、K增加了催化剂的碱性中心,促进了COS水解反应,提高了催化剂活性;Na、K优先与HCl反应生成金属氯化物,减弱了HCl对载体组分的氯化作用,提高了催化剂的抗氯性。探明了Na/Al₂O₃和K/Al₂O₃催化剂在含HCl气氛的失活机理。HCl占据了催化剂的中强碱性中心(M—O),与碱金属活性组分反应生成了金属氯化物(M—Cl),降低了催化剂的活性。Na/Al₂O₃催化剂在HCl气氛中的Na流失量显著低于K/Al₂O₃催化剂中K的流失量,提高了Na/Al₂O₃催化剂的抗氯性。
- 高炉煤气脱硫 /
- 催化水解 /
- 羰基硫 /
- 铝基催化剂 /
- 碱金属 /
- 氯化氢
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

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