Mechanism of elemental mercury oxidation over copper-based oxide catalysts: Kinetics and transient reaction studies

Mechanism of elemental mercury oxidation over copper-based oxide catalysts: Kinetics and transient reaction studies
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铜基氧化物催化剂上元素汞的氧化机理:动力学和瞬态反应研究

DOI:
10.1021/acs.iecr.9b04806
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发表时间:
2020-01
影响因子:
4.2
通讯作者:
Yang Shijian
Yang Shijian
中科院分区:
工程技术3区
文献类型:
--
作者:
Zhang Qi;Mei Jian;Sun Pengxiang;Zhao Hui;Guo Yongfu;Yang Shijian

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由于铜基氧化物对Hg-0的氧化机理较为复杂,有目的地提高其对Hg-0的氧化性能一直是一个难题。本研究从汞平衡、动力学和瞬态反应等方面对CuO/TiO 2催化剂上Hg-0的氧化机理进行了深入的研究。吸附在CuO/TiO 2上的HgO几乎不与气态HCl反应生成HgCl 2,因此CuO/TiO 2上HgO的氧化几乎不受Mars-Maessen机理的影响。He在300-400 ° C下在CuO/TiO 2上的氧化相对于气态Hg-0浓度的反应级数远小于1,因此Deacon机制和Eley-Rideal机制都不优于Hg-0在CuO/TiO 2上的氧化。由于其他三种机理对CuO/TiO 2上Hg-0氧化的贡献均被排除,因此CuO/TiO 2上Hg-0氧化主要遵循Langmuir-Hinshelwood机理,该机理可以合理地解释CuO/TiO 2上Hg-0氧化的所有实验现象。
Purposefully improving the performances of copper-based oxides for Hg-0 oxidation was beset with difficulties due to their vagueness of Hg-0 oxidation mechanism. In this study, Hg-0 oxidation mechanism over CuO/TiO2 was deeply investigated by Hg balance, kinetics, and transient reaction. HgO adsorbed on CuO/TiO2 scarcely reacted with gaseous HCl to form HgCl2, so the Mars-Maessen mechanism scarcely contributed to Hg-0 oxidation over CuO/TiO2. The reaction order of He oxidation over CuO/TiO2 at 300-400 degrees C with respect to the gaseous Hg-0 concentration was much less than 1, so neither the Deacon mechanism nor the Eley- Rideal mechanism predominated over Hg-0 oxidation over CuO/TiO2. As the contributions of other three mechanisms to Hg-0 oxidation over CuO/TiO2 were all ruled out, Hg-0 oxidation over CuO/TiO2 mainly followed the Langmuir-Hinshelwood mechanism, which can reasonably explain all the experimental phenomena of Hg-0 oxidation over CuO/TiO2.
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