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钒钨/二氧化钛催化剂在氨选择性催化还原一氧化氮过程中的失活机制新见解:砷与钾物种之间的协同作用

New insights into the deactivation mechanism of VO-WO/TiO catalyst during selective catalytic reduction of NO with NH: synergies between arsenic and potassium species.

作者信息

Li Lin, Chen Lin, Kong Ming, Liu Qingcai, Ren Shan

机构信息

Engineering Research Center for Energy and Environment of Chongqing, College of Materials Science and Engineering, Chongqing University Chongqing 400044 China

Chongqing Key Laboratory of Vanadium-Titanium Metallurgy and New Materials, Chongqing University Chongqing 400044 PR China.

出版信息

RSC Adv. 2019 Nov 19;9(65):37724-37732. doi: 10.1039/c9ra07545c.

DOI:10.1039/c9ra07545c
PMID:35541811
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC9075767/
Abstract

Synergies between arsenic (As) and potassium (K) species in the deactivation of VO-WO/TiO catalyst were investigated. Both arsenic oxide and potassium species presented a serious poisoning impact on catalyst activities, and the extent of poisoning of (As + K) was much stronger than their single superposition. The intrinsic reasons were explored and analyzed by N physisorption, XPS, H-TPR, NH-TPD, NH-DRIFTS and FTIR. Results indicated that BET surface area decreased due to the formation of a dense arsenic coating on the catalyst surface. V-OH active sites were destroyed by arsenic and As-OH acid sites were newly generated. After potassium species were added to arsenic-poisoned catalyst, K further neutralized the As-OH acid sites, and the amount and stability of both Lewis and BrØnsted acid sites decreased more greatly. Potassium also reacted with intermediate NH when the temperature was elevated to higher than 250 °C, which resulted in more NH consumption and NH-SCR reaction inhibition. The extent of deactivation was related to the potassium species when both poisons reacted on the catalyst, and the influence sequence followed AsKS < AsKN < AsKC. AsO + KSO presented the weakest impact among these three poisoned catalysts due to the resistance of SO to arsenic.

摘要

研究了砷(As)和钾(K)物种在VO-WO/TiO催化剂失活过程中的协同作用。氧化砷和钾物种均对催化剂活性产生严重中毒影响,且(As+K)的中毒程度远强于它们的简单叠加。通过N物理吸附、XPS、H-TPR、NH-TPD、NH-DRIFTS和FTIR对内在原因进行了探索和分析。结果表明,由于催化剂表面形成致密的砷涂层,BET表面积减小。V-OH活性位点被砷破坏,新生成了As-OH酸性位点。向砷中毒催化剂中添加钾物种后,K进一步中和了As-OH酸性位点,Lewis酸位点和Brønsted酸位点的数量和稳定性均有更大程度的降低。当温度升高到高于250℃时,钾还与中间产物NH发生反应,导致更多的NH消耗和NH-SCR反应受到抑制。当两种毒物在催化剂上发生反应时,失活程度与钾物种有关,影响顺序为AsKS<AsKN<AsKC。由于SO对砷的抗性,AsO+KSO在这三种中毒催化剂中表现出最弱的影响。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/201c/9075767/e6cf162ac12b/c9ra07545c-f8.jpg
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