Sm2O3/γ-Al2O3催化剂的COS催化水解性能及失活机制

doi:10.11949/0438-1157.20250068

化工学报 ›› 2025, Vol. 76 ›› Issue (8): 4061-4070.DOI: 10.11949/0438-1157.20250068

• 催化、动力学与反应器 • 上一篇下一篇

Sm₂O₃/γ-Al₂O₃催化剂的COS催化水解性能及失活机制

杨敏¹^,²(), 段新伟¹^,², 吴俊宏¹^,², 米杰¹^,², 王建成¹^,²^,³, 武蒙蒙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，山西太原 030024
^2.太原理工大学煤科学与技术教育部重点实验室，山西太原 030024
^3.太原理工大学环境科学与工程学院，山西晋中 030600

收稿日期:2025-01-16 修回日期:2025-02-24 出版日期:2025-08-25 发布日期:2025-09-17
通讯作者: 武蒙蒙
作者简介:杨敏（1999—），女，硕士研究生，yangmin990603@163.com
基金资助:
国家自然科学基金面上项目(22278294);山西省自然科学基金面上项目(20210302123191);中央引导地方科技发展资金项目(YDZJSX2025C006)

COS catalyzed hydrolysis performance and deactivation mechanism of Sm₂O₃/γ-Al₂O₃ catalysts

Min YANG¹^,²(), Xinwei DUAN¹^,², Junhong WU¹^,², Jie MI¹^,², Jiancheng WANG¹^,²^,³, Mengmeng WU¹^,²()

^1.State Key Laboratory of Clean and Efficient Coal Utilization, Taiyuan University of Technology, Taiyuan 030024, Shanxi, China
^2.Key Laboratory of Coal Science and Technology, Ministry of Education, Taiyuan University of Technology, Taiyuan 030024, Shanxi, China
^3.College of Environmental Science and Engineering, Taiyuan University of Technology, Jinzhong 030600, Shanxi, China

Received:2025-01-16 Revised:2025-02-24 Online:2025-08-25 Published:2025-09-17
Contact: Mengmeng WU

摘要/Abstract

摘要：

低温催化水解羰基硫（COS）是推动煤气洁净转化利用的关键技术之一。现代合成气经高温净化后COS含量低，但工业气源（如高炉和焦炉煤气）中COS含量较高（75~400 mg·m^-3）。因此，研究COS水解技术对工业煤气净化及未来合成气高效制备意义重大。前期研究发现，γ-Al₂O₃负载稀土金属在低浓度COS条件下表现出较强的催化水解活性，但其在低温和高浓度COS气氛下的催化水解行为尚不明确。本研究探讨了不同稀土金属氧化物（La₂O₃、Sm₂O₃和CeO₂）对γ-Al₂O₃催化水解行为的提升作用；并基于气体组成影响规律及多种结构表征，剖析了优选稀土金属与γ-Al₂O₃间的相互作用。结果表明：在70℃、1000 mg·m^-3 COS、3%（体积分数）H₂O及0.5%（体积分数）O₂条件下，负载Sm₂O₃（质量分数为5%）的改性催化剂（Sm₂O₃/γ-Al₂O₃）表现出最佳性能，反应8 h后H₂S选择性为86.3%，且COS转化率保持在90%以上，高于未改性γ-Al₂O₃（65.3%）。此外，Sm掺杂提高了抗H₂S中毒能力，归因于Sm改性增加了γ-Al₂O₃表面的碱性位点。CO₂的存在显著削弱了Sm₂O₃/γ-Al₂O₃对COS转化率的提升作用（降低39.6%），这是由于CO₂的竞争吸附导致催化剂失活，且该过程可逆。另外，在H₂S和CO₂共存条件下，CO₂优先吸附在催化剂表面，占据碱性位点使催化剂快速失活。

关键词: 低温催化, COS催化水解, 碱性位点, H₂S选择性

Abstract:

Low temperature catalytic hydrolysis of carbonyl sulfide (COS) is a key technology for promoting the clean conversion and utilization of gas. Modern syngas has low COS content after high temperature purification, but industrial gas sources (such as blast furnace and coke oven) have high COS content (75—400 mg·m^-3). Therefore, the study of COS hydrolysis technology is of great significance for industrial gas purification and efficient preparation of syngas in the future. Previous studies have shown that γ-Al₂O₃ loaded with rare earth metals exhibits strong catalytic hydrolysis activity under low COS concentrations, but its behavior under low temperature and high COS concentrations remains unclear. This study investigates the enhancement effects of different rare earth metal oxides (La₂O₃,Sm₂O₃ and CeO₂) on the catalytic hydrolysis behavior of γ-Al₂O₃. Based on the influence of gas composition and various structural characterizations, the interactions between the selected rare earth metals and γ-Al₂O₃ are analyzed. The results indicate that, under conditions of 70℃, 1000 mg·m^-3 COS, 3% H₂O and 0.5% O₂, the modified catalyst (Sm₂O₃/γ-Al₂O₃) with Sm₂O₃ (the mass fraction is 5%) loading shows the best performance. After 8 h of reaction, the selectivity of H₂S is 86.3%, and the COS conversion rate remains above 90%, which is higher than that of unmodified γ-Al₂O₃ (65.3%). Additionally, Sm doping enhances the resistance to H₂S poisoning, attributed to the increased basic sites on the surface of γ-Al₂O₃. The presence of CO₂ significantly weakens the effect of Sm₂O₃/γ-Al₂O₃ on COS conversion (reduced by 39.6%), which is due to the competitive adsorption of CO₂ leading to catalyst deactivation, and this process is reversible. In addition, under the coexistence of H₂S and CO₂, CO₂ preferentially adsorbs on the catalyst surface, occupies basic sites and rapidly deactivates the catalyst.

Key words: low temperature catalysis, COS catalytic hydrolysis, basic sites, H₂S selectivity

中图分类号:

TQ 546

杨敏, 段新伟, 吴俊宏, 米杰, 王建成, 武蒙蒙. Sm₂O₃/γ-Al₂O₃催化剂的COS催化水解性能及失活机制[J]. 化工学报, 2025, 76(8): 4061-4070.

Min YANG, Xinwei DUAN, Junhong WU, Jie MI, Jiancheng WANG, Mengmeng WU. COS catalyzed hydrolysis performance and deactivation mechanism of Sm₂O₃/γ-Al₂O₃ catalysts[J]. CIESC Journal, 2025, 76(8): 4061-4070.

图/表 11

图1 COS水解催化剂活性评价装置示意图1—气体质量流量控制器;2—水蒸气发生器;3—温度控制器;4—电加热炉;5—石英管反应器;6—催化剂;7—尾气处理装置;8—气相色谱Fig.1 Schematic diagram of COS hydrolysis catalyst activity evaluation device

图2 各催化剂对COS水解转化率（a）及H2S选择性（b）的影响

Fig.2 Effect of catalysts on COS hydrolysis conversion (a) and H2S selectivity (b)(70℃,200 ml·min-1,1000 mg·m-3 COS,3% H2O,0.5% O2,N2 balance)

图3 恒定CO2条件下催化剂的COS转化率及出口H2S与COS浓度变化（a）和暂态实验中CO2对COS转化率的影响（b）

Fig.3 COS conversion and H2S concentration at the outlet as a function of COS concentration under constant CO2 (a) and effect of CO2 on COS conversion in transient experiments (b)(70℃,200 ml·min-1,1000 mg·m-3 COS,3% H2O,0.5% O2,5% CO2,N2 balance)

图4 恒定H2S条件下催化剂的COS转化率及出口H2S与COS浓度变化（a）和暂态实验中H2S对COS转化率的影响（b）(70℃,200 ml·min-1,1000 mg·m-3 COS,3% H2O,0.5% O2,1000 mg·m-3 H2S, N2 balance)

Fig.4 COS conversion and H2S concentration at the outlet as a function of COS concentration under constant H2S (a) and effect of H2S on COS conversion in transient experiments (b)

图5 CO2和H2S气体组成下γ-Al2O3和Sm2O3/γ-Al2O3催化剂的COS转化率及H2S和COS出口浓度(70℃,200 ml·min-1,1000 mg·m-3 COS,3% H2O,0.5% O2,5% CO2,1000 mg·m-3 H2S,N2 balance)

Fig.5 COS conversion and H2S and COS outlet concentrations of Al2O3 and Sm2O3/γ-Al2O3 catalysts under CO2 and H2S conditions

图6 不同气体组成下γ-Al2O3和Sm2O3/γ-Al2O3催化剂的COS转化率及H2S选择性

Fig.6 COS conversion and H2S selectivity over Al2O3 and Sm2O3/γ-Al2O3 catalysts under different compositions

表1 不同气体组成下γ-Al2O3和Sm2O3/γ-Al2O3催化剂催化COS前后的孔结构参数

Table 1 Pore structure parameters of γ-Al2O3 and Sm2O3/γ-Al2O3 catalysts before and after COS catalysis under different gas compositions

反应条件	γ-Al₂O₃			Sm₂O₃/γ-Al₂O₃
反应条件	比表面积/(m²·g^-1)	孔体积/(cm³·g^-1)	平均孔径/nm	比表面积/(m²·g^-1)	孔体积/(cm³·g^-1)	平均孔径/nm
fresh	141.2	1.2	33.5	121.5	0.5	16.2
used（O₂）	141.2	0.5	15.1	124.6	0.5	15.9
used（O₂+CO₂）	133.9	0.5	15.3	121.1	0.5	16.5
used（O₂+H₂S）	112.0	0.5	16.6	113.9	0.5	16.8
used（O₂+CO₂+H₂S）	134.3	0.5	15.4	120.1	0.5	16.7

图7 不同气体组成下Al2O3和Sm2O3/γ-Al2O3催化剂在催化反应前后的XRD谱图

Fig.7 XRD patterns of Al2O3 and Sm2O3/γ-Al2O3 catalysts before and after catalysis reaction under different compositions

图8 不同气体组成下Al2O3和Sm2O3/γ-Al2O3催化反应前后的XPS图

Fig.8 XPS spectra of γ-Al2O3 and Sm2O3/γ-Al2O3 before and after catalysis reaction under different compositions

图9 γ-Al2O3和Sm2O3/γ-Al2O3催化反应前后的CO2-TPD曲线（a）和碱性中心分布（b）

Fig.9 CO2-TPD curves (a) and center of basicity distribution (b) before and after catalysis reaction by γ-Al2O3 and Sm2O3/γ-Al2O3

图10 不同气体组成下催化剂的COS水解反应路径

Fig.10 COS hydrolysis reaction pathways for catalysts under different gas compositions

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Sm₂O₃/γ-Al₂O₃催化剂的COS催化水解性能及失活机制

COS catalyzed hydrolysis performance and deactivation mechanism of Sm₂O₃/γ-Al₂O₃ catalysts

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