NiMnAlO/ZSM-5催化剂协同净化NO和乙酸乙酯性能研究

赵丹娅; 成越; 牛新宇; 郭静; 周集体; 赵玲

doi:10.13205/j.hjgc.202610015

NiMnAlO/ZSM-5催化剂协同净化NO和乙酸乙酯性能研究

doi: 10.13205/j.hjgc.202610015

赵丹娅¹,
成越¹,
牛新宇¹,
郭静¹,
周集体^1,2,
赵玲^1, ,

1. 内蒙古大学生态与环境学院, 呼和浩特 010031;
2. 大连理工大学工业生态与环境工程教育部重点实验室, 辽宁大连 116024

基金项目:

内蒙古自治区科技计划项目（2023YFHH0120，2025KYPT0121）；呼和浩特市研发投入激励项目（2025-规-研-1）

详细信息

作者简介:
赵丹娅（2001—），女，博士研究生，主要研究方向为大气污染控制。2734167993@qq.com

通讯作者:
赵玲（1981—），女，博士，教授，主要研究方向为大气污染控制。nmzhl@hotmail.com

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出版历程
- 收稿日期: 2026-07-20
- 网络出版日期: 2026-11-10

Synergistic purification performance of NiMnAlO/ZSM-5 catalyst for NO and ethyl acetate

1. College of Ecology and Environment, Inner Mongolia University, Hohhot 010031, China;
2. Key Laboratory of Industrial Ecology and Environmental Engineering, Ministry of Education, Dalian University of Technology, Dalian 116024, China

摘要

摘要: 针对工业烟气NO_x 与挥发性有机物（VOCs）协同治理过程中存在的反应条件不匹配，催化剂无法同时兼顾氧化还原反应等问题，将NiMnAlO氧化物负载于ZSM-5分子筛载体，构建了Ni₁Mn₅AlO/ZSM-5催化剂，以CO作为还原剂、乙酸乙酯为代表性VOCs，研究乙酸乙酯和NO在选择性催化还原（CO-SCR）与VOCs催化氧化耦合体系中的协同脱除性能。结果表明，Ni₁Mn₅AlO/ZSM-5催化剂兼具NO还原和乙酸乙酯氧化活性，其催化性能明显优于Ni₁Mn₅AlO和ZSM-5催化剂。通过调控ZSM-5硅铝比，优化得到的Ni₁Mn₅AlO/ZSM-5（硅铝比为41.7）催化剂在CO、NO、乙酸乙酯和O₂共存条件下，350 ℃时NO转化率为71.6%，乙酸乙酯氧化T₉₀为216 ℃。表征结果表明，复合催化剂呈现微孔-介孔复合结构，表面酸性位点数量明显增加；ZSM-5载体促进Mn³⁺活性物种形成，调控表面氧物种与氧空位分布，提高了催化剂的氧化还原性能。动力学分析和原位红外结果表明，CO作为还原剂促进了NO转化，同时维持催化剂表面氧化还原循环；乙酸乙酯在酸性位点作用下经含氧中间物种逐步氧化，实现了NO与VOCs的协同去除。研究为多污染物共存条件下双功能催化剂的设计及工业烟气协同净化提供了新思路。
- CO-SCR /
- 乙酸乙酯 /
- Ni₁Mn₅AlO/ZSM-5 /
- 协同净化
Abstract: To address the challenges associated with the synergistic removal of NO_x and volatile organic compounds （VOCs） from industrial exhaust gases， including the mismatch between reaction requirements and the lack of multifunctional catalysts， a bifunctional Ni₁Mn₅AlO/ZSM-5 catalyst was prepared by integrating NiMnAlO oxide with ZSM-5 zeolite. With CO as the reducing agent and ethyl acetate as a model VOC， the catalytic performance of the composite was evaluated in a coupled system integrating CO-SCR and VOCs catalytic oxidation. The results demonstrated that the Ni₁Mn₅AlO/ZSM-5 catalyst exhibited superior NO reduction and ethyl acetate oxidation activities compared with pristine Ni₁Mn₅AlO and ZSM-5. By optimizing the Si/Al ratio of ZSM-5， the Ni₁Mn₅AlO/ZSM-5（Si/Al ratio=41.7） catalyst achieved the best overall catalytic performance， delivering an NO conversion rate of 71.6% at 350 ℃ and a T₉₀ of 216 ℃ for ethyl acetate oxidation in a mixed atmosphere containing CO， NO， ethyl acetate， and O₂. Characterization results indicated that the composite catalyst exhibited a microporous-mesoporous structure， and the number of acidic sites on the catalyst surface was significantly enhanced. Meanwhile， the ZSM-5 support regulated the electronic structure of Ni and Mn species， promoted the formation of Mn³⁺ active species， and optimized the balance between surface oxygen species and oxygen vacancies， thereby enhancing the redox capability of the catalyst. Kinetic analysis and in situ FTIR results indicated that CO acted as a reducing agent in the CO-SCR process to promote NO conversion while maintaining the surface redox cycle of the catalyst. Ethyl acetate was activated on acidi sites and subsequently oxidized through oxygen-containing intermediates， enabling the synergistic removal of NO and VOCs. This study provides new insights into the design of bifunctional catalysts for the simultaneous purification of multiple pollutants in complex industrial exhaust gases.
- CO-SCR /
- ethyl acetate /
- NiMnAlO/ZSM-5 /
- synergistic purification

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参考文献(37)

[1]	ERICKSON E L,NEWMARK L G,HIGGINS J M,et al. Nitrogen oxides and ozone in urban air:a review of 50 plus years of progress[J]. Environmental Progress & Sustainable Energy,2020,39（6）:13484.
[2]	HE C,CHENG J,ZHANG X,et al. Recent advances in the catalytic oxidation of volatile organic compounds:a review based on pollutant sorts and sources[J]. Chemical Reviews,2019,119（7）:4471-4568.
[3]	LIU B,JI J,ZHANG B,et al. Catalytic ozonation of VOCs at low temperature:a comprehensive review[J]. Journal of Hazardous Materials,2022,422:126847.
[4]	WANG C,WANG H,WANG X,et al. Combined catalytic conversion of NO_x and VOCs:present status and prospects[J]. Catalysts,2023,13（2）:295.
[5]	ZHOU X,XIE J,ZHANG R,et al. Recent advances in different catalysts for synergistic removal of NO_x and VOCs:a minor review[J]. Journal of Environmental Chemical Engineering,2024,12（1）:111764.
[6]	TIAN Z,DING X,PAN H,et al. A review of simultaneous catalytic removal of NO_x and VOCs:from mechanism to modification strategy[J]. Catalysts,2025,15（12）:1114.
[7]	LI M,WANG R. Combined catalytic conversion of NO_x and VOCs:present status and prospects[J]. Materials,2025,18（1）:39.
[8]	ZHANG Y,WANG X,LI J,et al. Development of ozone reactivity scales for volatile organic compounds in a Chinese megacity[J]. Atmospheric Environment,2020,224:117309.
[9]	LI S,XU T,HUI S,et al. Emission of volatile organic compounds（VOCs）during coal combustion at different heating rates[J]. Fuel,2018,225:554-562.
[10]	ZHAI Z X,MENG J,WANG G,et al. Emission characteristics and characteristic substance identification of volatile odorous organic compounds from organic solvent-using enterprises[J]. Environmental Science,2018,39（8）:3557-3562. 翟增秀,孟洁,王亘,等. 有机溶剂使用企业挥发性恶臭有机物排放特征及特征物质识别[J]. 环境科学,2018,39（8）:3557-3562.
[11]	ZHENG S,ZHANG Y,YANG Y,et al. Effects of biofuels on soot and NO formation during gasoline combustion[J]. Energy & Fuels,2022,36（19）:12054-12062.
[12]	DAI G,LIU B,WANG R,et al. Pretreatment techniques in CO-SCR and NH₃-SCR:status,challenges,and perspectives[J]. Journal of Catalysis,2025,442:115925.
[13]	LIAN D,CHEN M,WANG H,et al. Promising selective catalytic reduction of NO_x by CO:status,challenges,and perspective[J]. Chemical Engineering Journal,2024,496:154242.
[14]	ZHOU Y,GAO F,YI L,et al. CoCeO_x-PVP catalyst for effective CO-SCR in the presence of O₂[J]. Molecules,2025,30（5）:1133.
[15]	ZHAN M N,YU S B,LI T Y,et al. Review on the catalytic technologies for simultaneous removal of multiple air pollutants[J]. Journal of Environmental Chemical Engineering,2026,14（2）:121614.
[16]	HAN S J,LI Z J,XIAO Y,et al. NO_x regime-dependent effects of biogenic emissions on toluene degradation and product formation[J]. Journal of Environmental Sciences,2026,140:230-242.
[17]	LI J X,ZHAO R,SUN M Q,et al. Collaborative effect of in-plasma catalysis with sequential Na₂SO₃ wet scrubbing on co-elimination of NO_x and VOCs from simulated sinter flue gas[J]. Processes,2023,11（10）:2916.
[18]	LI Z,XIAO J W,GAO Y S,et al. Design of bifunctional Cu-SSZ-13@Mn₂Cu₁Al₁O _x core-shell catalyst with superior activity for the simultaneous removal of VOCs and NO_x[J]. Environmental Science & Technology,2023,57（48）:20326-20338.
[19]	ZHANG Y P,ZHU Y N,FAN Y M,et al. Highly active nanostick-assembled TiO₂@MnO _x hollow-sphere structure for photothermocatalysis of ethyl acetate and NO with free-ammonia at low temperature:resistence,key reaction steps and mechanisms[J]. Applied Surface Science,2023,607:154887.
[20]	LIANG Z J,LI S L,YANG Q,et al. Recent advances in CO selective catalytic reduction technology:catalyst reaction mechanisms and antitoxic strategies research[J]. Journal of Environmental Chemical Engineering,2025,13（6）:120122.
[21]	LI R Y,LIU Z P,LI J H,et al. Advances in CO-SCR of NO_x in the presence of oxygen:strategies,reaction mechanisms,and key influencing factors[J]. Separation and Purification Technology,2026,359:131483.
[22]	LI Y H,ZHANG H R,XUE X J,et al. Insights into Mn-N synergism in activated carbon-based catalysts for low-temperature NH₃-SCR of NO_x[J]. Journal of Environmental Chemical Engineering,2025,13（5）:118573.
[23]	YAN Q H,XIAO J W,GUI R R,et al. Insights into enhancement of NH₃-SCR activity and N₂ selectivity of LDHs-derived NiMnAlO _x catalysts:combination of experiments and DFT calculations[J]. Applied Catalysis B:Environmental,2024,343:123489.
[24]	MORANKAR D,BARHATE K,HATVATE N T,et al. ZSM-5 zeolite:structural features,catalytic properties,and multidisciplinary applications in organic synthesis,material science,and environmental remediation[J]. Coordination Chemistry Reviews,2026,487:217245.
[25]	GAO Y,ZHENG B H,WU G,et al. Effect of the Si/Al ratio on the performance of hierarchical ZSM-5 zeolites for methanol aromatization[J]. RSC Advances,2016,6（87）:83581-83588.
[26]	ZHAO W,XU Y N,QIAO Y H,et al. The design of core-shell ZSM-5@NiAl-LDH composites for efficient adsorption of VOCs under high humidity[J]. Separation and Purification Technology,2025,355:129729.
[27]	石壹军. 高性能 VOCs 氧化催化剂 Pt-CeO₂-TiO₂/ZSM-5 的设计与制备[D]. 杭州:浙江大学,2023. SHI Y J. Design and preparation of high-performance VOCs oxidation catalyst Pt-CeO₂-TiO₂/ZSM-5[D]. Hangzhou:Zhejiang University,2023.
[28]	GOU J,ZHANG P F,LI W J,et al. Effects of different modification methods on ZSM-5 zeolite[J]. Shandong Chemical Industry,2022,51（20）:65-68. 苟晋,张鹏飞,李文杰,等. 不同改性方法对 ZSM-5 分子筛的影响[J]. 山东化工,2022,51（20）:65-68.
[29]	ZHANG F,GUTIÉRREZ R A,LUSTEMBERG P G,et al. Metal-support interactions and C1 chemistry:transforming Pt-CeO₂ into a highly active and stable catalyst for the conversion of carbon dioxide and methane[J]. ACS Catalysis,2021,11（3）:1613-1623.
[30]	GARZON F P,BLUM T,CHI M F,et al. Tunability of low-temperature strong metal-support interactions（SMSI）for enhanced catalysis[J]. Abstracts of Papers of the American Chemical Society,2020,258:5.
[31]	DANIEL S,OTIENO H N,LIAQAT A,et al. Unraveling structure-activity-acidity relationships in transition metal-modified ZSM-5 catalysts for complete propane oxidation[J]. Journal of Environmental Chemical Engineering,2025,13（4）:117240.
[32]	LEMAIRE P,de REVIERE A,SHARMA D,et al. The influence of mesopore architecture in hierarchical H-ZSM-5 on n-butanol dehydration[J]. ACS Engineering Au,2025,5（4）:434-449.
[33]	WANG Z R,GAO L,ZHONG X,et al. Accurately tuning the pore size and acidity of mesoporous zeolites for enhancing the catalytic hydrocracking of polypropylene[J]. Journal of Materials Chemistry A,2025,13（4）:2875-2883.
[34]	KOLTSAKIDIS S,KOIDI V,LAPPAS A,et al. Influence of binder concentration in zeolitic ZSM-5/bentonite 3D-printed monoliths manufactured through robocasting for catalytic applications[J]. The International Journal of Advanced Manufacturing Technology,2023,126（1/2）:259-271.
[35]	MUDAU T L,SADARE O O,IWARERE S A,et al. CO conversion to liquid fuel over a bi-functional Co/H-ZSM-5 catalyst:effect of support desilication and catalyst promotion[J]. Chemical Engineering Communications,2025,212（12）:1896-1913.
[36]	ZHANG B X,ZHANG J L,SHI J B,et al. Manganese acting as a high-performance heterogeneous electrocatalyst in carbon dioxide reduction[J]. Nature Communications,2019,10（1）:2980.
[37]	GUO R Y,LIU C R,YANG Y,et al. Insight into Ni active site coordination in nickel-manganese spinels for methanol electrooxidation catalysis[J]. Chemical Science,2025,16（29）:13514-13519.