

浏览全部资源
扫码关注微信
中石化石油化工科学研究院有限公司,北京 100083
Received:23 March 2026,
Revised:2026-04-27,
Online First:26 June 2026,
移动端阅览
朱莹,李博.NH3-SCR催化剂水热失活机制与水热稳定性提升策略研究进展[J].低碳化学与化工,DOI:10.12434/j.issn.2097-2547.20260136.
ZHU Ying,LI Bo.Research progress on hydrothermal deactivation mechanisms of NH3-SCR catalysts and strategies to enhance their hydrothermal stabilities[J].Low-Carbon Chemistry and Chemical Engineering,DOI:10.12434/j.issn.2097-2547.20260136.
朱莹,李博.NH3-SCR催化剂水热失活机制与水热稳定性提升策略研究进展[J].低碳化学与化工,DOI:10.12434/j.issn.2097-2547.20260136. DOI:
ZHU Ying,LI Bo.Research progress on hydrothermal deactivation mechanisms of NH3-SCR catalysts and strategies to enhance their hydrothermal stabilities[J].Low-Carbon Chemistry and Chemical Engineering,DOI:10.12434/j.issn.2097-2547.20260136. DOI:
在重型柴油车国六排放标准技术路线中,柴油颗粒捕集器(DPF)的主动再生会使后端的NH
3
选择性催化还原(NH
3
-SCR)催化剂处于高温水热环境中。因此,开发在该条件下综合性能稳定的催化剂具有重要的应用价值。系统综述了NH
3
-SCR催化剂的水热失活机制与稳定性提升策略。首先,聚焦分子筛催化剂,分析了水热老化导致的骨架脱铝与活性金属物种迁移聚集的协同失活机制;随后,针对金属氧化物催化剂,阐述了载体相变、活性相结晶和表面活性位点损失的热失活本质。在此基础上,从分子筛组成优化、助剂添加和骨架结构调控等方面,总结了提升水热稳定性的主要策略。最后,对未来高水热稳定性NH
3
-SCR催化剂的开发前景进行了展望。
In the technical approach to meeting the China VI emission standards for heavy-duty diesel vehicles
the active regeneration of diesel particulate filter (DPF) subjects the downstream ammonia selective catalytic reduction (NH
3
-SCR) catalysts to a high-temperature hydrothermal environment. Therefore
developing catalyst with stable comprehensive performance under such conditions holds significant application value. The hydrothermal deactivation mechanisms and stability enhancement strategies of NH
3
-SCR catalysts were systematically reviewed. Firstly
focusing on zeolite catalysts
the synergistic deactivation mechanism caused by hydrothermal aging
which involves framework dealumination
migration and aggregation of active metal species
was analyzed. Subsequently
for metal oxide catalysts
the intrinsic thermal deactivation essence
which includes carrier phase transformation
active phase crystallization and loss of surface active sites was elucidated. Based on this
the main strategies for enhancing hydrothermal stability were summarized
including zeolite composition optimization
additive addition and framework structure regulation. Finally
the development prospects of NH
3
-SCR catalysts with high hydrothermal stabilities in the future were prospected.
中华人民共和国生态环境部 . 中国移动源环境管理年报 [R ] . 北京 : 中华人民共和国生态环境部 , 2025 .
Ministry of Ecology and Environment of the People’s Republic of China . China mobile source environmental management annual report [R ] . Beijing : Ministry of Ecology and Environment of the People’s Republic of China , 2025 .
DUNCAN B N , LAMSAL L N , THOMPSON A M , et al . A space-based, high-resolution view of notable changes in urban NO x pollution around the world (2005—2014) [J ] . Journal of Geophysical Research: Atmospheres , 2016 , 121 ( 2 ): 976 - 996 .
BONINGARI T , SMIRNIOTIS P G . Impact of nitrogen oxides on the environment and human health: Mn-based materials for the NO x abatement [J ] . Current Opinion in Chemical Engineering , 2016 , 13 : 133 - 141 .
RICHTER A , BURROWS J P , NÜSS H , et al . Increase in tropospheric nitrogen dioxide over China observed from space [J ] . Nature , 2005 , 437 ( 7055 ): 129 - 132 .
中华人民共和国生态环境部 . 重型柴油车污染物排放限值及测量方法(中国第六阶段) : GB 17691—2018 [S ] . 北京 : 中国环境科学出版社 , 2018 .
Ministry of Ecology and Environment of the People’s Republic of China . Limits and measurement methods for emissions from diesel fuelled heavy-duty vehicles (China VI) : GB 17691—2018 [S ] . Beijing : China Environmental Science Press , 2018 .
SHAN Y L , DU J P , ZHANG Y , et al . Selective catalytic reduction of NO x with NH 3 : Opportunities and challenges of Cu-based small-pore zeolites [J ] . National Science Review , 2021 , 8 ( 10 ): nwab010 .
QI G S , WANG Y H , YANG R T . Selective catalytic reduction of nitric oxide with ammonia over ZSM-5 based catalysts for diesel engine applications [J ] . Catalysis Letters , 2008 , 121 : 111 - 117 .
BRANDENBERGER S , KRӦCHER O , TISSLER A , et al . The state of the art in selective catalytic reduction of NO x by ammonia using metal-exchanged zeolite catalysts [J ] . Catalysis Reviews: Science and Engineering , 2008 , 50 : 492 - 531 .
LIU F D , SHAN W P , PAN D W , et al . Selective catalytic reduction of NO x by NH 3 for heavy-duty diesel vehicles [J ] . Chinese Journal of Catalysis , 2014 , 35 : 1438 - 1445 .
DAMMA D , ETTIREDDY P R , REDDY B M , et al . A review of low temperature NH 3 -SCR for Removal of NO x [J ] . Catalysts , 2019 , 9 : 349 .
NOVA I , DALL’ACQUA L , LIETTI L , et al . Study of Thermal deactivation of a de-NO x commercial catalyst [J ] . Applied Catalysis B: Environmental , 2001 , 35 : 31 - 42 .
XU W Q , YU Y B , ZHANG C B , et al . Selective catalytic reduction of NO by NH 3 over a Ce/TiO 2 catalyst [J ] . Catalysis Communications , 2008 , 9 ( 6 ): 1453 - 1457 .
SHAN W P , LIU F D , YU Y B , et al . The use of ceria for the selective catalytic reduction of NO x with NH 3 [J ] . Chinese Journal of Catalysis , 2014 , 35 : 1251 - 1259 .
GAO X , JIANG Y , FU Y C , et al . Preparation and characterization of CeO 2 /TiO 2 catalysts for selective catalytic reduction of NO with NH 3 [J ] . Catalysis Communications , 2010 , 11 ( 5 ): 465 - 469 .
HAN L P , CAI S X , GAO M , et al . Selective catalytic reduction of NO x with NH 3 by using novel catalysts: State of the art and future prospects [J ] . Chemical Reviews , 2019 , 119 ( 19 ): 10916 - 10976 .
郑伟 , 陈佳玲 , 郭立 , 等 . 金属负载型分子筛催化剂在NH 3 -SCR反应中水热稳定性的研究进展 [J ] . 燃料化学学报 , 2020 , 48 ( 10 ): 1193 - 1207 .
ZHENG W , CHEN J L , GUO L , et al . Research progress of hydrothermal stability of metal-based zeolite catalysts in NH 3 -SCR reaction [J ] . Journal of Fuel Chemistry and Technology , 2020 , 48 ( 10 ): 1193 - 1207 .
LIU J J , SHI X Y , SHAN Y L , et al . Hydrothermal stability of CeO 2 -WO 3 -ZrO 2 mixed oxides for selective catalytic reduction of NO x by NH 3 [J ] . Environmental Science & Technology , 2018 , 52 ( 20 ): 11769 - 11777 .
XU G Y , GUO X L , CHENG X X , et al . A review of Mn-based catalysts for low-temperature NH 3 -SCR: NO x removal and H 2 O/SO 2 resistance [J ] . Nanoscale , 2021 , 13 : 7052 .
LIU Q , BIAN C , MING S J , et al . The opportunities and challenges of iron-zeolite as NH 3 -SCR catalyst in purification of vehicle exhaust [J ] . Applied Catalysis A , General, 2020 , 607 : 117865 .
OU Q , ZHU M H , YANG Z X , et al . Pathway regulation of carbon dioxide hydrogenation on iron-based-zeolite bifunctional catalysts [J ] . Applied Catalysis B: Environment and Energy , 2024 , 357 : 124211 .
SU W K , LI Z G , PENG Y , et al . Correlation of the changes in the framework and active Cu sites for typical Cu/CHA zeolites (SSZ-13 and SAPO-34) during hydrothermal aging [J ] . Physical Chemistry Chemical Physics , 2015 , 17 ( 43 ): 29142 - 29149 .
ZHAO H W , ZHAO Y N , LIU M K , et al . Phosphorus modification to improve the hydrothermal stability of a Cu-SSZ-13 catalyst for selective reduction of NO x with NH 3 [J ] . Applied Catalysis B: Environmental , 2019 , 252 : 230 - 239 .
BRANDENBERGER S , KRӦCHER O , CASAPU M , et al . Hydrothermal deactivation of Fe-ZSM-5 catalysts for the selective catalytic reduction of NO with NH 3 [J ] . Applied Catalysis B: Environmental , 2011 , 101 : 649 - 659 .
LI S H , KONG H Y , ZHANG W P . A density functional theory modeling on the framework stability of Al-rich Cu-SSZ-13 zeolite modified by metal ions [J ] . Industrial & Engineering Chemistry Research , 2020 , 59 : 5675 - 5685 .
PAOLUCCI C , PAREKHarekh A A , KHURANAhurana I , et al . Catalysis in a cage: Condition-dependent speciation and dynamics of exchanged Cu cations in SSZ-13 zeolites [J ] . Journal of the American Chemical Society , 2026 , 138 : 6028 - 6048 .
SONG J , WANG Y , WALTER E D , et al . Toward rational design of Cu/SSZ-13 selective catalytic reduction catalysts: Implications from atomic-level understanding of hydrothermal stability [J ] . ACS Catalysis , 2017 , 7 ( 12 ): 8214 - 8227 .
KRӦCHER O , DEVADAS M , ELSENER M , et al . Investigation of the selective catalytic reduction of NO by NH 3 on Fe-ZSM5 monolith catalysts [J ] . Applied Catalysis B: Environmental , 2006 , 66 ( 3/4 ): 208 - 216 .
IWASAKI M , YAMAZAKI K , BANNO K , et al . Characterization of Fe/ZSM-5 DeNO x catalysts prepared by different methods: Relationships between active Fe sites and NH 3 -SCR performance [J ] . Journal of Catalysis , 2008 , 260 ( 2 ): 205 - 216 .
BRANDENBERGER S , KRӦCHER O , TISSLER A , et al . Estimation of the fractions of different nuclear iron species in uniformly metal-exchanged Fe-ZSM-5 samples based on a poisson distribution [J ] . Applied Catalysis A: General , 2010 , 373 ( 1/2 ): 168 - 175 .
KOVARIK L , WASHTON N M , KUKKADAPU R , et al . Transformation of active sites in Fe/SSZ-13 SCR catalysts during hydrothermal aging: A spectroscopic, microscopic, and kinetics study [J ] . ACS Catalysis , 2017 , 7 ( 4 ): 2458 - 2470 .
HAN S , CHENG J , ZHENG C K , et al . Effect of Si/Al ratio on catalytic performance of hydrothermally aged Cu-SSZ-13 for the NH 3 -SCR of NO in simulated diesel exhaust [J ] . Applied Surface Science , 2017 , 419 : 382 - 392 .
MING S J , YU S Q , PANG L , et al . Regulation of Si/Al ratios of Fe-SSZ-13: Impact on NH 3 -SCR activity and hydrothermal stability [J ] . Applied Surface Science , 2024 , 654 : 159492 .
SHAN Y L , DU J P , YU Y B , et al . Precise control of post-treatment significantly increases hydrothermal stability of in-situ synthesized Cu-zeolites for NH 3 -SCR reaction [J ] . Applied Catalysis B: Environmental , 2020 , 266 : 118655 .
SHI X Y , LIU F D , SHAN W P , et al . Hydrotherma l deactivation of Fe-ZSM-5 prepared by different methods for the selective catalytic reduction of NO x with NH 3 [J ] . Chinese Journal of Catalysis , 2012 , 33 ( 2/3 ): 454 - 464 .
WANG L , XU S D , HE S X , et al . Rational construction of metal nanoparticles fixed in zeolite crystals as highly efficient heterogeneous catalysts [J ] . Nano Today , 2018 , 20 : 74 - 83 .
WANG X Y , LIU F , XU Z Y , et al . Mn modified Cu-SSZ-13 catalysts with excellent NH 3 -SCR activity and hydrothermal stability [J ] . Journal of Environmental Chemical Engineering , 2025 , 13 : 117421 .
CHEN Z , LIU Q , GUO L , et al . The promoting mechanism of in situ Zr doping on the hydrothermal stability of Fe-SSZ-13 catalyst for NH 3 -SCR reaction [J ] . Applied Catalysis B: Environmental , 2021 , 286 : 119816 .
XU R N , WANG Z Y , LIU N , et al . Understanding Zn functions on hydrothermal stability in a one-pot-synthesized Cu & Zn-SSZ-13 catalyst for NH 3 selective catalytic reduction [J ] . ACS Catalysis , 2020 , 10 : 6197 - 6212 .
SHEN T , DU J P , YAN Y , et al . Y-doped Cu-SSZ-13 synthesized via one-step method with superior catalytic activity and hydrothermal stability for NH 3 -SCR reaction [J ] . Journal of Rare Earths , 2026 , 44 : 220 - 229 .
CHEN M Y , ZHAO W R , WEI Y Z , et al . Improving the hydrothermal stability of Al-rich Cu-SSZ-13 zeolite via Pr-ion modification [J ] . Chemical Science , 2024 , 15 : 5548 .
ZHANG Y B , WANG P , ZHAO H Y , et al . The promoting mechanism of Ce on the hydrothermal stability of Fe-beta catalyst for NH 3 -SCR reaction [J ] . Microporous and Mesoporous Materials , 2022 , 338 : 111937 .
GAO F , WANG Y L , WASHTON N M , et al . Effects of alkali and alkaline earth cocations on the activity and hydrothermal stability of Cu/SSZ-13 NH 3 -SCR catalysts [J ] . ACS Catalysis , 2015 , 5 ( 11 ): 6780 - 6791 .
CUI Y R , WANG Y L , MEI D H , et al . Revisiting effects of alkali metal and alkaline earth co-cation additives to Cu/SSZ-13 selective catalytic reduction catalysts [J ] . Journal of Catalysis , 2019 , 378 : 363 - 375 .
XIE L J , LIU F D , SHI X Y , et al . Effects of post-treatment method and Na co-cation on the hydrothermal stability of Cu-SSZ-13 catalyst for the selective catalytic reduction of NO x with NH 3 [J ] . Applied Catalysis B: Environmental , 2015 , 179 : 206 - 212 .
ZHAO Z C , YU R , ZHAO R R , et al . Cu-exchanged Al-rich SSZ-13 zeolite from organotemplate-free synthesis as NH 3 -SCR catalyst: Effects of Na + ions on the activity and hydrothermal stability [J ] . Applied Catalysis B: Environmental , 2017 , 217 : 421 - 428 .
KAKIUCHI Y , TANIGAWA T , TSUNOJI N , et al . Phosphorus modified small-pore zeolites and their catalytic performances in ethanol conversion and NH 3 -SCR reactions [J ] . Applied Catalysis A: General , 2019 , 575 : 204 - 213 .
LV W T , SUN F M , JIAO W Y , et al . Construction of core-shell structure Cu-SSZ-13 catalyst for boosting its NH 3 -SCR activity and hydrothermal stability [J ] . Catalysis Science & Technology , 2025 , 15 , 3762 .
HAN J F , LI J Y , BAI Y , et al . Cocrystallized zeolite interface boosting the hydrothermal stability of Cu-CHA/OFF-ERI catalysts [J ] . CCS Chemistry , 2025 , 7 : 681 - 690 .
MAGNUSSON M , FRIDELL E , INGELSTEN H H . The influence of sulfur dioxide and water on the performance of a marine SCR catalyst [J ] . Applied Catalysis B: Environmental , 2012 , 111/112 : 20 - 26 .
REN D D , GUI K T , GU S C , et al . Mechanism of improving the SCR NO removal activity of Fe 2 O 3 catalyst by doping Mn [J ] . Journal of Alloys and Compounds , 2021 , 867 : 158787 .
CHEN Y F , LI J L , TENG W X , et al . Revealing the effect of electronic interaction between dual redox sites on CeO 2 -Fe 2 O 3 NH 3 -SCR catalyst through interface contact tailoring [J ] . Fuel , 2023 , 353 : 129179 .
ZHANG Z Q , LI J T , TIAN J , et al . The effects of Mn-based catalysts on the selective catalytic reduction of NO x with NH 3 at low temperature: A review [J ] . Fuel Processing Technology , 2022 , 230 : 107213 .
SALEH R Y , WACHS I E , CHAN S S , et al . The interaction of V 2 O 5 with TiO 2 (anatase): Catalyst evolution with calcination temperature and O-xylene oxidation [J ] . Journal of Catalysis , 1986 , 98 : 102 .
ZHU M H , LAI J K , TUMULURI U , et al . Nature of active sites and surface intermediates during SCR of NO with NH 3 by supported V 2 O 5 -WO 3 /TiO 2 catalysts [J ] . Journal of the American Ceramic Society , 2017 , 139 : 15624 - 15627 .
LAI J K , WACHS I E . A perspective on the selective catalytic reduction (SCR) of NO with NH 3 by supported V 2 O 5 -WO 3 /TiO 2 catalysts [J ] . ACS Catalysis , 2018 , 8 ( 7 ): 6537 - 6551 .
HE G Z , LIAN Z H , YU Y B , et al . Polymeric vanadyl species determine the low-temperature activity of V-based catalysts for the SCR of NO x with NH 3 [J ] . Science Advances , 2018 , 4 : eaau4637 .
YAN Z D , SHAN W P , SHI X Y , et al . The way to enhance the thermal stability of V 2 O 5 -based catalysts for NH 3 -SCR [J ] . Catalysis Today , 2020 , 355 : 408 - 414 .
CASANOVA M , SCHERMANZ K , LLORCA J , et al . Improved high temperature stability of NH 3 -SCR catalysts based on rare earth vanadates supported on TiO 2 -WO 3 -SiO 2 [J ] . Catalysis Today , 2012 , 184 ( 1 ): 227 - 236 .
VARGAS M A L , CASANOVA M , TROVARELLI A , et al . An IR study of thermally stable V 2 O 5 -WO 3 -TiO 2 SCR catalysts modified with silica and rare-earths (Ce, Tb, Er) [J ] . Applied Catalysis B: Environmental , 2007 , 75 ( 3/4 ): 303 - 311 .
MARBERGER A , FERRI D , ELSENER M , et al . Relationship between structures and activities of supported metal vanadates for the selective catalytic reduction of NO by NH 3 [J ] . Applied Catalysis B: Environmental , 2017 , 218 : 731 - 742 .
LIU X S , CHEN H F , WU X D , et al . Effects of SiO 2 modification on the hydrothermal stability of the V 2 O 5 /WO 3 -TiO 2 NH 3 -SCR catalyst: TiO 2 structure and vanadia species [J ] . Catalysis Science & Technology , 2019 , 9 ( 14 ): 3711 - 3720 .
SI W Z , LIU H Y , YAN T , et al . Sn-doped rutile TiO 2 for vanadyl catalysts: Improvements on activity and stability in SCR reaction [J ] . Applied Catalysis B: Environmental , 2020 , 269 : 118797 .
CHEN H F , XIA Y , FANG R Y , et al . The effects of tungsten and hydrothermal aging in promoting NH 3 -SCR activity on V 2 O 5 /WO 3 -TiO 2 catalysts [J ] . Applied Surface Science , 2018 , 459 : 639 - 646 .
SHI A J , WANG X Q , YU T , et al . The effect of zirconia additive on the activity and structure stability of V 2 O 5 /WO 3 -TiO 2 ammonia SCR catalysts [J ] . Applied Catalysis B: Environmental , 2011 , 106 ( 3-4 ): 359 - 369 .
SCHMITT R , NENNING A , KRAYNIS O , et al . A review of defect structure and chemistry in ceria and its solid solutions [J ] . Chemical Society Reviews , 2020 , 49 : 554 .
蔡彦迪 , 纪小雨 , 张弼凤 , 等 . 铈基催化剂用于NH 3 选择性催化氧化的研究进展 [J ] . 中国科学: 化学 , 2024 , 54 ( 3 ): 295 - 308 .
CAI Y D , JI X Y , ZHANG B F , et al . Research progress in ceria-based catalysts for the selective catalytic oxidation of NH 3 [J ] . Scientia Sinica Chimica , 2024 , 54 ( 3 ): 295 - 308 .
FORNASIERO P , KAŠPAR J , SERGO V , et al . Redox behavior of high-surface-area Rh-, Pt-, and Pd-loaded Ce 0.5 Zr 0.5 O 2 mixed oxide [J ] . Journal of Catalysis , 1999 , 182 ( 1 ): 56 - 69 .
SHAN W P , LIU F D , HE H , et al . The remarkable improvement of a Ce-Ti based catalyst for NO x abatement, prepared by a homogeneous precipitation method [J ] . ChemCatChem , 2011 , 3 ( 8 ): 1286 - 1289 .
SHAN W P , LIU F D , HE H , et al . An environmentally-benign CeO 2 -TiO 2 catalyst for the selective catalytic reduction of NO x with NH 3 in simulated diesel exhaust [J ] . Catalysis Today , 2012 , 184 ( 1 ): 160 - 165 .
LI Z G , LI J H , LIU S X , et al . Ultra hydrothermal stability of CeO 2 -WO 3 /TiO 2 for NH 3 -SCR of NO compared to traditional V 2 O 5 -WO 3 /TiO 2 catalyst [J ] . Catalysis Today , 2015 , 258 : 11 - 16 .
刘晶晶 . Ce基氧化物催化剂NH 3 -SCR活性及热稳定性研究 [D ] . 北京 : 中国科学院大学 , 2020 .
LIU J J . NH 3 -SCR activity and thermal stability of Ce-based oxide catalysts [D ] . Beijing : University of Chinese Academy of Sciences , 2020 .
QU R Y , PENG Y , SUN X X , et al . Identification of the reaction pathway and reactive species for the selective catalytic reduction of NO with NH 3 over cerium-niobium oxide catalysts [J ] . Catalysis Science & Technology , 2016 , 6 ( 7 ): 2136 - 2142 .
DING S P , LIU F D , SHI X Y , et al . Promotional effect of Nb additive on the activity and hydrothermal stability for the selective catalytic reduction of NO x with NH 3 over CeZrO x catalyst [J ] . Applied Catalysis B: Environmental , 2016 , 180 : 766 - 774 .
LIU J J , HE G Z , SHAN W P , et al . Introducing tin to develop ternary metal oxides with excellent hydrother mal stability for NH 3 selective catalytic reduction of NO x [J ] . Applied Catalysis B: Environmental , 2021 , 291 : 120125 .
ZHU Y , LIU J J , HE G Z , et al . Remarkable enhancement of the activity and hydrothermal stability of a CeO 2 -based NH 3 -SCR Catalyst by Sn modification [J ] . Engineering , 2025 , 48 : 141 - 150 .
LIU S , LIN Q J , LIU J Y , et al . Enhancement of the hydrothermal stability of WO 3 /Ce 0.68 Zr 0.32 O 2 catalyst by silica modification for NH 3 -SCR [J ] . ASC Applied Energy Materials , 2020 , 3 , 1161 - 1170 .
LIU S , LIU J Y , LIN Q J , et al . Solvent effects on the low-temperature NH 3 -SCR activity and hydrothermal stability of WO 3 /SiO 2 @CeZrO x catalyst [J ] . ACS Sustainable Chemistry & Engineering , 2020 , 8 , 13418 - 13429 .
SHAN W P , YU Y B , ZHANG Y , et al . Theory and practice of metal oxide catalyst design for the selective catalytic reduction of NO x with NH 3 [J ] . Catalysis Today , 2021 , 376 : 292 - 301 .
0
Views
0
下载量
0
CNKI被引量
Publicity Resources
Related Articles
Related Author
Related Institution
蜀公网安备51012202001533