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FeOx 添加对机械化学法制备的钒基催化剂去除真实 PCDD/Fs 的促进作用及机理研究。

Promoting effect of FeOx addition on the mechanochemically prepared vanadium-based catalyst for real PCDD/Fs removal and mechanism insight.

机构信息

State Key Laboratory for Clean Energy Utilization, Institute for Thermal Power Engineering, Zhejiang University, Hangzhou 310027, China.

State Key Laboratory for Clean Energy Utilization, Institute for Thermal Power Engineering, Zhejiang University, Hangzhou 310027, China.

出版信息

J Environ Sci (China). 2024 Mar;137:478-487. doi: 10.1016/j.jes.2022.11.023. Epub 2022 Dec 7.

DOI:10.1016/j.jes.2022.11.023
PMID:37980032
Abstract

Industrial-use VOx-based catalysts usually have a higher active temperature window (> 250-300°C), which becomes a "bottleneck" for the practical application of PCDD/Fs catalytic degradation technology. In this work, VOx-FeOx/TiO catalyst prepared via mechanochemically method was investigated for the catalytic removal of PCDD/Fs. The removal efficiency of 1,2-DCBz, pure PCDD/Fs gas generated in the lab, PCDD/Fs from actual flue gas, long-term were studied, and the degradation mechanism was explored using FTIR and TOFMS. The degradation efficiency of 1,2-DCBz and PCDD/Fs on VOx-FeOx/TiO were higher than that of VOx/TiO catalyst, and the optimal FeOx addition ratio was 3 wt.%. The characterization results show that the addition of FeOx can effectively improve the pore structure, surface acidity, and VOx dispersion of the catalyst, thus contributing to increasing the V content and surface-active oxygen, which is conducive to the improvement of adsorption and redox performance of the catalyst. Under the actual MSWI (municipal solid waste incineration) flue gas, the PCDD/Fs removal efficiency over VTi-3Fe-MC maintained long-term stability, higher than 85% for 240 min. This result was not significantly reduced compared with the data obtained in the laboratory. According to the analysis results of intermediate products by FTIR and GC-TOFMS, it can be inferred that the epoxidation fracture of benzene ring is the rate-limiting step of dioxin catalytic degradation reaction. This work gives an in-depth view into the PCDD/Fs removal over VOx-FeOx/TiO catalysts and could provide guidelines for the rational design of reliable catalysts for industrial applications.

摘要

工业用 VOx 基催化剂通常具有更高的活性温度窗口(>250-300°C),这成为 PCDD/Fs 催化降解技术实际应用的“瓶颈”。在这项工作中,通过机械化学法制备的 VOx-FeOx/TiO 催化剂用于催化去除 PCDD/Fs。研究了 1,2-DCBz、实验室产生的纯 PCDD/Fs 气体、实际烟道气中的 PCDD/Fs 的去除效率,并通过 FTIR 和 TOFMS 探讨了降解机制。VOx-FeOx/TiO 上 1,2-DCBz 和 PCDD/Fs 的降解效率高于 VOx/TiO 催化剂,最佳 FeOx 添加比例为 3wt%。表征结果表明,添加 FeOx 可以有效改善催化剂的孔结构、表面酸度和 VOx 分散性,从而增加 V 含量和表面活性氧,有利于提高催化剂的吸附和氧化还原性能。在实际 MSWI(城市固体废物焚烧)烟气条件下,VOx-Ti-3Fe-MC 对 PCDD/Fs 的去除效率保持长期稳定,240min 内高于 85%。与实验室获得的数据相比,这一结果没有明显降低。根据 FTIR 和 GC-TOFMS 对中间产物的分析结果,可以推断出苯环的环氧化断裂是二恶英催化降解反应的限速步骤。这项工作深入研究了 VOx-FeOx/TiO 催化剂对 PCDD/Fs 的去除,并为工业应用中可靠催化剂的合理设计提供了指导。

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