TiAl基羰基硫水解催化剂的中毒机制与抗氧性能研究

doi:10.11949/0438-1157.20220883

摘要/Abstract

摘要：

高炉煤气脱硫是实现钢铁行业多工序全流程超低排放的关键。高炉煤气中主要有机硫组分是羰基硫（COS），常用γ-Al₂O₃基催化剂水解脱除，但是其抗氧性能有待提高。采用共沉淀法制备了Ti_0.5Al和K_0.2Ti_0.5Al催化剂，考察了催化剂在含氧气氛下的COS水解催化性能，并分析了氧体积分数对COS转化率和H₂S产率的影响规律。活性测试结果表明，Ti_0.5Al催化剂的初始COS转化率接近90%，随着反应时间增长效率逐渐降低至60%以下；K_0.2Ti_0.5Al催化剂在0.5% （体积分数） O₂的气氛下持续反应22 h后，其COS转化率仍可保持在93.44%。表征结果显示，催化剂失活后比表面积大幅减小，表面碱性显著减弱。此外，活性中心Al原子硫酸化是导致催化剂失活的主要原因，而硫酸盐的沉积为次要原因。原位红外结果表明，K的引入可显著减弱O₂在催化剂表面的吸附，并且阻断中间过渡物种的氧化，这是K提高催化剂抗氧性能的关键。

关键词: 高炉煤气, 羰基硫, 催化水解, 氧中毒, 原位红外

Abstract:

Desulfurization of blast furnace gas is the key to achieving ultra-low emissions in the steel industry with multiple processes and the entire process. In this paper, Ti_0.5Al and K_0.2Ti_0.5Al catalysts were prepared by co-precipitation method, and the catalytic performance of COS hydrolysis under oxygen-containing atmosphere was investigated. Besides, the effect law of oxygen volume fraction on COS conversion and H₂S selectivity was analyzed. A series of characterization methods were used to systematically investigate the physicochemical properties of the catalysts before and after deactivation, and the effect of O₂ on the mechanism of COS hydrolysis reaction was investigated by in situ DRIFTS simulation. The activity test results showed that the initial COS conversion of Ti_0.5Al catalyst was close to 90% while the efficiency gradually decreased to below 60% as the reaction time increased. As a comparison, the COS conversion of the K_0.2Ti_0.5Al catalyst could still be maintained at 93.44% after 22 h of continuous reaction under 0.5% (vol) O₂ atmosphere. The characterization results showed that the specific surface area is greatly reduced after deactivation, and the surface basicity is significantly weakened. In addition, sulfation of the active center Al atoms was the main cause of catalyst deactivation, while sulfate deposition was a secondary cause. The in situ DRIFTS results showed that the introduction of K significantly attenuated the adsorption of O₂ on the catalyst surface and blocked the oxidation of intermediate transition species, which were the key for K to improve the antioxidant performance of the catalyst.

Key words: blast furnace gas, carbonyl sulfide, catalytic hydrolysis, oxygen poisoning, in situ DRIFTS

中图分类号:

X 511

黄俊, 刘羿良, 吴鹏, 沈凯, 张亚平. TiAl基羰基硫水解催化剂的中毒机制与抗氧性能研究[J]. 化工学报, 2022, 73(10): 4461-4471.

Jun HUANG, Yiliang LIU, Peng WU, Kai SHEN, Yaping ZHANG. Poisoning mechanism and antioxidant performance of TiAl-based carbonyl sulfur hydrolysis catalyst[J]. CIESC Journal, 2022, 73(10): 4461-4471.

图/表 14

图1 COS水解催化剂活性评价装置的结构

Fig.1 Structure of COS hydrolysis catalyst activity evaluation device

图2 Ti0.5Al和K0.2Ti0.5Al催化剂在含氧气氛中的COS水解活性

Fig.2 COS hydrolysis reactivity of Ti0.5Al and K0.2Ti0.5Al catalysts in O2-containing atmosphere

图3 K0.2Ti0.5Al催化剂在不同含氧气氛中的COS水解活性

Fig.3 COS hydrolysis reactivity of K0.2Ti0.5Al catalysts in different O2-containing atmosphere

图4 新鲜和失活K0.2Ti0.5Al催化剂的结构特性

Fig.4 Textural properties of fresh and used K0.2Ti0.5Al catalysts

表1 新鲜和失活K0.2Ti0.5Al催化剂的BET比表面积、孔容和孔径

Table 1 BET specific surface area and pore properties of fresh and used catalysts

样品	比表面积/(m²/g)	孔体积/(cm³/g)	孔径/nm
新鲜	152.42	0.26	7.48
失活	71.17	0.16	8.36

图5 新鲜和失活K0.2Ti0.5Al催化剂的XRD谱图

Fig.5 XRD patterns of fresh and used K0.2Ti0.5Al catalysts

图6 K0.2Ti0.5Al催化剂的SEM图像与EDS能谱

Fig.6 SEM images and EDS results of K0.2Ti0.5Al catalyst

表2 新鲜和失活K0.2Ti0.5Al催化剂表面元素含量

Table 2 Surface element content of fresh and used K0.2Ti0.5Al catalyst

样品	含量/%
样品	C	O	Al	S	K	Ti	总量
新鲜	—	51.60	21.30	未检出	8.41	18.68	100
失活	60.10	26.55	5.88	0.25	1.82	5.40	100

图7 新鲜和失活K0.2Ti0.5Al催化剂的CO2-TPD谱图

Fig.7 The CO2-TPD results of fresh and used K0.2Ti0.5Al catalysts

图8 失活催化剂的S 2p轨道XPS谱图

Fig.8 The XPS spectra of the deactived catalysts on S 2p

图9 失活催化剂的TG-DTG曲线

Fig.9 The TG-DTG curve of the deactive K0.2Ti0.5Al catalyst

图10 COS在预吸附O2的催化剂表面的反应红外谱图（T=125℃）

Fig.10 The DRIFTS spectra of COS react with pre-adsorbed O2 over catalysts at 125℃

图11 O2在预吸附COS的催化剂表面的反应红外谱图(T=125℃)

Fig.11 The DRIFTS spectra of O2 react with pre-adsorbed COS over catalysts at 125℃

图12 COS与O2在催化剂表面同步吸附反应的红外谱图（T=125℃）

Fig.12 The DRIFTS spectra of O2 react with COS over catalysts at 125℃

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