化工学报 ›› 2022, Vol. 73 ›› Issue (10): 4461-4471.DOI: 10.11949/0438-1157.20220883
收稿日期:
2022-06-24
修回日期:
2022-09-09
出版日期:
2022-10-05
发布日期:
2022-11-02
通讯作者:
张亚平
作者简介:
黄俊(1970—),男,工程师,huangjun0722@126.com
基金资助:
Jun HUANG1(), Yiliang LIU2, Peng WU2, Kai SHEN2, Yaping ZHANG2()
Received:
2022-06-24
Revised:
2022-09-09
Online:
2022-10-05
Published:
2022-11-02
Contact:
Yaping ZHANG
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Ti0.5Al和K0.2Ti0.5Al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,Ti0.5Al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;K0.2Ti0.5Al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。
中图分类号:
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.
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 |
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 |
样品 | 含量/% | ||||||
---|---|---|---|---|---|---|---|
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 |
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/% | ||||||
---|---|---|---|---|---|---|---|
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 |
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