非贵金属改性钒钛基催化剂NH3-SCR脱硝协同控制VOCs

doi:10.16085/j.issn.1000-6613.2023-0885

摘要/Abstract

摘要：

在钒钛基催化剂上分别负载四种非贵金属（Ce、Cu、Mn、Fe），研究改性催化剂对中低温选择性催化还原（SCR）脱硝协同挥发性有机物（VOCs）催化氧化的性能。对四种负载金属（Ce、Cu、Mn、Fe）分别进行SCR脱硝和VOCs催化氧化，发现Ce改性的催化剂在低温段具有良好的SCR脱硝活性和VOCs催化氧化性能，被认为具有良好的协同催化潜力。之后对Ce掺杂改性催化剂进行协同评价研究，发现在275~300℃的温度区间内，3V-5Ce/Ti催化剂的NO转化率和VOCs转化率可达到100%。并分别比较了SCR反应协同VOC与未协同VOC时N₂的选择性和CO₂的选择性，发现在低温段时甲苯的引入会显著降低N₂选择性，而随着温度升高，N₂O副产物的产生，N₂的选择性恢复到未引入甲苯时。同时发现协同反应时CO₂的选择性有明显下降。对3V-5Ce/Ti催化剂的SEM、XRD、XPS、NH₃-TPD表征说明Ce的引入不会破坏载体形貌，可以为催化剂提高更多表面氧空位，从而提高催化剂的氧化还原性能，并提供更多弱酸位点作为反应位点。抗硫抗水及稳定性测试表明3V-5Ce/Ti催化剂具有良好的抗硫抗水性和稳定性。

关键词: 选择性催化还原, 挥发性有机构, 非贵金属, 催化剂, 协同催化

Abstract:

We loaded a variety of non-noble metal(Ce、Cu、Mn、Fe) on vanadium and titanium based catalysts, and studied the performance of the modified catalysts for the selective catalytic reduction (SCR) denitrification and the catalytic oxidation of volatile organic compounds (VOCs). The Ce modified catalyst showed good SCR denitrification activity and VOCs catalytic oxidation performance in the low temperature section, indicating its good cooperative catalytic potential. As for the Ce doping modified catalyst, the NO conversion rate and VOCs conversion rate over 3V-5Ce/Ti catalyst could reach 100% within the temperature range of 275—300℃. We compared the selectivity of N₂ and CO₂ between SCR-VOC and SCR alone, and found that the introduction of toluene significantly reduced N₂ selectivity, which however was restored to the level without toluene after temperature rise. It was also found that a significant decrease in the selectivity of CO₂ during the synergistic reaction. The SEM, XRD, XPS, NH₃-TPD characterization of 3V-5Ce/Ti catalyst showed that the introduction of Ce provided more surface oxygen vacancies and more weak acid sites as reaction sites on the catalyst without changing the carrier morphology, and thus improved the redox performance of the catalyst. The resistance to water and stability tests showed that 3V-5Ce/Ti catalyst has good sulfur resistance, water resistance and stability.

Key words: selective catalytic reduction (SCR), volatile organic compounds (VOCs), non-noble metal, catalyst, concerted catalysis

中图分类号:

R139⁺.1

邓丽萍, 时好雨, 刘霄龙, 陈瑶姬, 严晶颖. 非贵金属改性钒钛基催化剂NH₃-SCR脱硝协同控制VOCs[J]. 化工进展, 2023, 42(S1): 542-548.

DENG Liping, SHI Haoyu, LIU Xiaolong, CHEN Yaoji, YAN Jingying. Non-noble metal modified vanadium titanium-based catalyst for NH₃-SCR denitrification simultaneous control VOCs[J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 542-548.

图/表 11

图1 活性评价平台示意图

图2 钒钛基催化剂SCR脱硝效率评价（NO为500μL/L，NH3为500μL/L，GHSV为110000)

图3 钒钛基催化剂甲苯催化氧化效率评价（C7H8为100μL/L，GHSV为110000h-1）

图4 3V-5Ce/Ti催化剂XRD表征图

图5 Ce催化剂的XPS表征

图6 Ce掺杂催化剂的SEM及EDS表征

图7 3V-5Ce/Ti催化剂与3V/Ti催化剂的NH3-TPD图

图8 3V-5Ce/Ti催化剂SCR脱硝协同甲苯催化氧化活性评价（NO为500μL/L，NH3为500μL/L，C7H8为50μL/L，GHSV为110000h-1）

图9 协同反应对N2选择性的影响及副产物种类

图10 协同反应对3V-5Ce/Ti催化剂CO2选择性的影响

图11 含硫含水气氛下3V-5Ce/Ti催化剂的稳定性评价（NO为500μL/L，NH3为500μL/L，C7H8为50μL/L，SO2为50μL/L，H2O为10%，GHSV为110000h-1）

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非贵金属改性钒钛基催化剂NH₃-SCR脱硝协同控制VOCs

Non-noble metal modified vanadium titanium-based catalyst for NH₃-SCR denitrification simultaneous control VOCs

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