柴油车尾气氧化催化剂硫磷中毒研究进展

摘要/Abstract

摘要： 柴油车尾气氧化催化剂（DOC）是柴油车污染物排放后处理系统的重要组成部分，主要作用是有效去除未完全燃烧产生的一氧化碳（CO）和碳氢化合物（HC），并将部分一氧化氮（NO）氧化为二氧化氮（NO₂），促进后续柴油颗粒捕集器（DPF）再生和氨选择性催化还原（NH₃-SCR）反应。但在实际运行时，处于整个后处理系统最前端的DOC不可避免地会受到柴油以及润滑油中硫化物和磷化物的毒化，从而影响催化剂后处理的净化效率。本文从硫磷对DOC催化性能的影响、硫磷中毒机制和缓解硫磷中毒策略3个方面详细综述了DOC催化剂硫、磷及硫磷复合中毒的研究进展，并针对DOC硫、磷中毒的科学研究与实际应用之间存在的差距，展望了未来抗硫磷中毒DOC催化剂的发展方向。

关键词: 柴油车, 尾气氧化催化剂, 硫磷中毒, 中毒机制, 缓解中毒策略

Abstract: Diesel vehicle exhaust oxidation catalyst (DOC) is an important part of diesel vehicle emission post-treatment system. Its main function is to effectively remove carbon monoxide (CO) and hydrocarbons (HC) caused by incomplete combustion, and oxidize a portion of nitric oxide (NO) to nitrogen dioxide (NO₂), which promotes the subsequent regeneration of diesel particulate filters (DPF) and ammonia selective catalytic reduction (NH₃-SCR) reactions. However, in practical operation, the DOC, which is located at the forefront of the entire after treatment system for diesel emission, inevitably suffers from sulfides and phosphates in diesel and lubricating oil, which affects the overall purification efficiency of the after treatment system. In this paper, the effects of sulfur and phosphorus on the catalytic performance of DOC, the mechanism of sulfur and phosphorus poisoning, and strategies for mitigating sulfur and phosphorus poisoning were reviewed in detail. In view of gap between scientific research and practical applications of DOC for sulfur and phosphorus poisoning, the development direction of DOC for sulfur and phosphorus poisoning in the future was prospected.

Key words: diesel vehicle, exhaust oxidation catalyst, sulfur-phosphorus complex poisoning, mechanism of poisoning, strategy for mitigating poisoning

刘丛玮王猛张燕单文坡. 柴油车尾气氧化催化剂硫磷中毒研究进展[J]. 石油炼制与化工, 2024, 55(2): 23-35.

参考文献

[1]交通运输部.2022年交通运输行业发展统计公报 [M/OL]. 2023. https://xxgk.mot.gov.cn/2020/jigou/zhghs/202306/t20230615_3847023.html. [2]中华人民共和国生态环境部.中国移动源环境管理年报 [M/OL]. 2022. https://www.mee.gov.cn/ywdt/xwfb/202212/t20221207_1007157.shtml. [3]单文坡, 余运波, 张燕.中国重型柴油车后处理技术研究进展[J].环境科学研究, 2019, 32(10):1672-7 [4]Russell A, Epling W S.Diesel Oxidation Catalysts[J].Catalysis Reviews: Science and Engineerin, 2011, 53(4):337-423 [5]Grossale A, Nova I, Tronconi E.NH3-NO/NO2 SCR for Diesel exhausts aftertreatment: reactivity, mechanism and modelling of a commercial zeolite based catalysts Iron and Cupper promoted; proceedings of the CAPoC 8, Eighth International Congress on Catalysis and Automotive Pollution Control, F, 2009 [C]. A. [6]Zhang Y, Lou D, Tan P, et al.Effect of SCR downsizing and ammonia slip catalyst coating on the emissions from a heavy-duty diesel engine [J]. Energy Reports, 2022, 8: 749-57. [7]王建强, 王远, 刘双喜.柴油车氧化催化技术研究进展[J].科技导报, 2012, 30(25):68-73 [8]Karre A V, Garlapalli R K, Jena A, et al.State of the art developments in oxidation performance and deactivation of diesel oxidation catalyst (DOC) [J]. Catalysis Communications, 2023, 179: [9]Yang W, Gong J, Wang X, et al.A Review on the Impact of SO2 on the Oxidation of NO,Hydrocarbons,and CO in Diesel Emission Control Catalysis[J].ACS Catalysis, 2021, 11(20):12446-68 [10]Zhang Z, Tian J, Li J, et al.The development of diesel oxidation catalysts and the effect of sulfur dioxide on catalysts of metal-based diesel oxidation catalysts: A review [J]. Fuel Processing Technology, 2022, 233: 107317. [11]Sharma H N, Suib S L, Mhadeshwar A B.Interactions of Sulfur Oxides with Diesel Oxidation Catalysts (DOCs) [M]. Novel Materials for Catalysis and Fuels Processing. 2013: 117-55. [12]Neyestanaki A K, Klingstedt F, Salmi T, et al.Deactivation of postcombustion catalysts,a review[J].Fuel, 2004, 83(4-5):395-408 [13]Wu Y, Zhang S, Hao J, et al.On-road vehicle emissions and their control in China: A review and outlook [J]. Sci Total Environ, 2017, 574: 332-49. [14]生态环境部和国家市场监督管理总局.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 [M]. 中国环境科学出版社. 2018: 1-357. [15]Kim Y-S, Lim S J, Kim Y H, et al.The role of doped Fe on the activity of alumina-supported Pt and Pd diesel exhaust catalysts[J].Research on Chemical Intermediates, 2011, 38(3-5):947-55 [16]Kro?cher O, Widmer M, Elsener M, et al.Adsorption and desorption of SOx on diesel oxidation catalysts[J].Industrial & Engineering Chemistry Research, 2009, 48(22):9847-57 [17]Bunting B G, More K, Lewis S, et al., 0148-7191 [R]: SAE Technical Paper, 2005. [18]Yang H, Wei G, Wang X, et al.Regeneration of SO2-poisoned diesel oxidation Pd/CeO2 catalyst [J]. Catalysis Communications, 2013, 36: 5-9. [19]Kolli T, Huuhtanen M, Hallikainen A, et al.The Effect of Sulphur on the Activity of PdAl2O3,PdCeO2 and PdZrO2 Diesel Exhaust Gas Catalysts[J].Catalysis Letters, 2008, 127(1-2):49-54 [20]Huang H, Jiang B, Gu L, et al.Promoting effect of vanadium on catalytic activity of Pt/Ce–Zr–O diesel oxidation catalysts [J]. Journal of Environmental Sciences, 2015, 33: 135-42. [21]Franken T, Vieweger E, Klimera A, et al.Sulphur tolerant diesel oxidation catalysts by noble metal alloying [J]. Catalysis Communications, 2019, 129: 105732. [22]Wan J, Ran R, Li M, et al.Effect of acid and base modification on the catalytic activity of Pt/Al2O3 for propene oxidation [J]. Journal of Molecular Catalysis A: Chemical, 2014, 383-384: 194-202. [23]Russell A, Henry C, Currier N W, et al.Spatially resolved temperature and gas species concentration changes during C3H6 oxidation over a PtAl2O3 catalyst following sulfur exposure[J].Applied Catalysis A: General, 2011, 397(1-2):272-84 [24]Kolli T, Kanerva T, Huuhtanen M, et al.The activity of PtAl2O3 diesel oxidation catalyst after sulphur and calcium treatments[J].Catalysis Today, 2010, 154(3-4):303-7 [25]Honkanen M, Huuhtanen M, K?rkk?inen M, et al.Characterization of Pt-based oxidation catalyst – Deactivated simultaneously by sulfur and phosphorus [J]. Journal of Catalysis, 2021, 397: 183-91. [26]Ho P H, Shao J, Yao D, et al.The effect of PtPd ratio on the oxidation activity and resistance to sulfur poisoning for Pt-PdBEA diesel oxidation catalysts with high siliceous content[J].Journal of Environmental Chemical Engineering, 2022, 10(4):108217- [27]Smirnov M Y, Kalinkin A V, Pashis A V, et al.Interaction of SO2 with Pt Model Supported Catalysts Studied by XPS[J].The Journal of Physical Chemistry C, 2014, 118(38):22120-35 [28]Sharma H N, Sun Y, Glascoe E A.Microkinetic modeling of H2SO4 formation on Pt based diesel oxidation catalysts [J]. Applied Catalysis B: Environmental, 2018, 220: 348-55. [29]Lang W, Laing P, Cheng Y, et al.Co-oxidation of CO and propylene on Pd/CeO2-ZrO2 and Pd/Al2O3 monolith catalysts: A light-off, kinetics, and mechanistic study [J]. Applied Catalysis B: Environmental, 2017, 218: 430-42. [30]Wilburn M S, Epling W S.Formation and Decomposition of Sulfite and Sulfate Species on PtPd Catalysts: An SO2 Oxidation and Sulfur Exposure Study[J].ACS Catalysis, 2018, 9(1):640-8 [31]Sharma H N, Sharma V, Mhadeshwar A B, et al.Why Pt Survives but Pd Suffers From SOx Poisoning?[J].J Phys Chem Lett, 2015, 6(7):1140-8 [32]Auvray X, Pingel T, Olsson E, et al.The effect gas composition during thermal aging on the dispersion and NO oxidation activity over Pt/Al2O3 catalysts [J]. Applied Catalysis B: Environmental, 2013, 129: 517-27. [33]Banerjee A M, Pai M R, Tewari R, et al.A comprehensive study on Pt/Al2O3 granular catalyst used for sulfuric acid decomposition step in sulfur–iodine thermochemical cycle: Changes in catalyst structure, morphology and metal-support interaction [J]. Applied Catalysis B: Environmental, 2015, 162: 327-37. [34]Hamzehlouyan T, Sampara C, Li J, et al.Sulfur Poisoning of a PtAl2O3 Oxidation Catalyst: Understanding of SO2,SO3 and H2SO4 Impacts[J].Topics in Catalysis, 2016, 59(10-12):1028-32 [35]Andersson J, Antonsson M, Eurenius L, et al.Deactivation of diesel oxidation catalysts: Vehicle- and synthetic aging correlations[J].Applied Catalysis B: Environmental, 2007, 72(1-2):71-81 [36]Cabello Galisteo F, Mariscal R, López Granados M, et al.Reactivation of sulphated PtAl2O3 catalysts by reductive treatment in the simultaneous oxidation of CO and C3H6[J].Applied Catalysis B: Environmental, 2007, 72(3-4):272-81 [37]Wiebenga M H, Kim C H, Schmieg S J, et al.Deactivation mechanisms of PtPd-based diesel oxidation catalysts[J].Catalysis Today, 2012, 184(1):197-204 [38]Li Y, Shen M, Wang J, et al.Influence of sulfation and regeneration on PtAl2O3 for NO oxidation[J].Catalysis Science & Technology, 2015, 5(3):1731-40 [39]Luo J-Y, Kisinger D, Abedi A, et al.Sulfur release from a model PtAl2O3 diesel oxidation catalyst: Temperature-programmed and step-response techniques characterization[J].Applied Catalysis A: General, 2010, 383(1-2):182-91 [40]Wilburn M S, Epling W S.SO2 adsorption and desorption characteristics of bimetallic Pd-Pt catalysts: Pd:Pt ratio dependency [J]. Catalysis Today, 2019, 320: 11-9. [41]Wilburn M S, Epling W S.SO2 adsorption and desorption characteristics of Pd and Pt catalysts: Precious metal crystallite size dependence [J]. Applied Catalysis A: General, 2017, 534: 85-93. [42]Yang Y, Wang G, Yang M, et al.Pt modulates the electronic structure of Pd to improve the performance of Pd-based catalytic combustion catalyst[J].International Journal of Hydrogen Energy, 2021, 46(35):18391-400 [43]Ho P H, Woo J-W, Feizie Ilmasani R, et al.The role of Pd–Pt Interactions in the Oxidation and Sulfur Resistance of Bimetallic Pd–Ptγ-Al2O3 Diesel Oxidation Catalysts[J].Industrial & Engineering Chemistry Research, 2021, 60(18):6596-612 [44]Zhang X, Liu Y, Deng J, et al.Catalytic performance and SO2 resistance of zirconia-supported platinum-palladium bimetallic nanoparticles for methane combustion [J]. Catalysis Today, 2022, 402: 138-48. [45]Shen M, Lin F, Wei G, et al.Improved sulfur-resistant ability on CO oxidation of PdCe075Zr0.25O2 over PdCeO2-TiO2 and PdCeO2[J].Journal of Rare Earths, 2015, 33(1):56-61 [46]Kim M-Y, Kyriakidou E A, Choi J-S, et al.Enhancing low-temperature activity and durability of Pd-based diesel oxidation catalysts using ZrO2 supports [J]. Applied Catalysis B: Environmental, 2016, 187: 181-94. [47]Zhang N, Yang Z, Chen Z, et al.Synthesis of Sulfur-Resistant TiO2-CeO2 Composite and Its Catalytic Performance in the Oxidation of a Soluble Organic Fraction from Diesel Exhaust[J].Catalysts, 2018, 8(6):246- [48]Yang Z, Zhang N, Cao Y, et al.Effect of yttria in PtTiO2 on sulfur resistance diesel oxidation catalysts: enhancement of low-temperature activity and stability[J].Catal Sci Technol, 2014, 4(9):3032-43 [49]Zhou J, Li G, Li H, et al.Pt@TiO /TiO2 as a highly effective and stable recipe for C3H8 and C3H6 combustion [J]. Fuel, 2023, 343: 128014. [50]Gu L, Chen X, Zhou Y, et al.Propene and CO oxidation on PtCe-Zr-SO42– diesel oxidation catalysts: Effect of sulfate on activity and stability[J].Chinese Journal of Catalysis, 2017, 38(3):607-15 [51]Wu X, Liu S, Weng D.Effects of tungsten oxide on soot oxidation activity and sulfur poisoning resistance of PtAl2O3 catalyst[J].Catalysis Science & Technology, 2011, 1(4):644-51 [52]Xia M, Liu Y, Li L, et al.A DFT study on PtMo resistance to SO2 poisoning[J].Science China Chemistry, 2013, 56(7):1004-8 [53]Xie S, Wang J, He H.Poisoning effect of sulphate on the selective catalytic reduction of NO by C3H6 over Ag-PdAl2O3[J].Journal of Molecular Catalysis A: Chemical, 2007, 266(1-2):166-72 [54]Millo F, Rafigh M, Andreata M, et al.Impact of high sulfur fuel and de-sulfation process on a close-coupled diesel oxidation catalyst and diesel particulate filter [J]. Fuel, 2017, 198: 58-67. [55]Agote-Arán M, Jacobsen V V, Elsener M, et al.Thermal Sintering and Phosphorus Poisoning of a Layered Diesel Oxidation Catalyst[J].Topics in Catalysis, 2022, 66(13-14):777-86 [56]Agote-Arán M, Elsener M, Schütze F W, et al.Understanding the impact of poison distribution on the performance of Diesel oxidation catalysts [J]. Applied Catalysis B: Environmental, 2021, 299: 120684. [57]Wang A, Wang J, Sheti S, et al.A deactivation mechanism study of phosphorus-poisoned diesel oxidation catalysts: model and supplier catalysts[J].Catalysis Science & Technology, 2020, 10(16):5602-17 [58]V?liheikki A, K?rkk?inen M, Honkanen M, et al.Deactivation of Pt/SiO2-ZrO2 diesel oxidation catalysts by sulphur, phosphorus and their combinations [J]. Applied Catalysis B: Environmental, 2017, 218: 409-19. [59]Ho P H, Shao J, Yao D, et al.Role of the supports during phosphorus poisoning of diesel oxidation catalysts [J]. Chemical Engineering Journal, 2023, 468: 143548. [60]Winkler A, Ferri D, Hauert R.Influence of aging effects on the conversion efficiency of automotive exhaust gas catalysts[J].Catalysis Today, 2010, 155(1-2):140-6 [61]Matam S K, Kondratenko E V, Aguirre M H, et al.The impact of aging environment on the evolution of Al2O3 supported Pt nanoparticles and their NO oxidation activity [J]. Applied Catalysis B: Environmental, 2013, 129: 214-24. [62]Honkanen M, K?rkk?inen M, Heikkinen O, et al.The Effect of Phosphorus Exposure on Diesel Oxidation Catalysts—Part II: Characterization of Structural Changes by Transmission Electron Microscopy[J].Topics in Catalysis, 2015, 58(14-17):971-6 [63]Agote-Arán M, Elsener M, Schütze F W, et al.On the relevance of P poisoning in real-world DOC aging [J]. Applied Catalysis B: Environmental, 2021, 291: 120062. [64]K?rkk?inen M, Kolli T, Honkanen M, et al.The Effect of Phosphorus Exposure on Diesel Oxidation Catalysts—Part I: Activity Measurements,Elementary and Surface Analyses[J].Topics in Catalysis, 2015, 58(14-17):961-70 [65]Hazlett M J, Moses-Debusk M, Parks J E, et al.Kinetic and mechanistic study of bimetallic Pt-Pd/Al2O3 catalysts for CO and C3H6 oxidation [J]. Applied Catalysis B: Environmental, 2017, 202: 404-17. [66]Bergman S L, Granestrand J, Xi S, et al.Probing the OxidationReduction Dynamics of Fresh and P-,Na-,and K-Contaminated PtPdAl2O3 Diesel Oxidation Catalysts by STEM,TPR,and in Situ XANES[J].The Journal of Physical Chemistry C, 2020, 124(5):2945-52 [67]Beckmann R, Engeler W, Mueller E, et al.A New Generation of Diesel Oxidation Catalysts [M]. SAE International. 1992. [68]Kr?ger V, Hietikko M, Angove D, et al.Effect of phosphorus poisoning on catalytic activity of diesel exhaust gas catalyst components containing oxide and Pt[J].Topics in Catalysis, 2007, 42-43(1-4):409-13 [69]Matam S K, Winkler A, Weidenkaff A, et al.Observations on the Aging Environment Dependent NO Oxidation Activity of Model PtAl2O3 Diesel Oxidation Catalyst[J].Topics in Catalysis, 2013, 56(1-8):329-32 [70]Anguita P, García-Vargas J M, Gaillard F, et al.Effect of Na, K, Ca and P-impurities on diesel oxidation catalysts (DOCs) [J]. Chemical Engineering Journal, 2018, 352: 333-42. [71]Anguita P, Gaillard F, Iojoiu E, et al.Study of hydrothermal aging impact on Na- and P-modified diesel oxidation catalyst (DOC) [J]. Journal of Catalysis, 2019, 375: 329-38. [72]赵旭腾, 侯进, 王一男.钯基催化剂氧化低浓度甲烷的研究进展[J].能源环境保护, 2023, 37(02):106-16 [73]蔡洁莹, 李杰, 张燕.甲烷燃烧催化剂研究进展[J].能源环境保护, 2023, 37(02):62-72 [74]Zhang G, Chen J, Wu Y, et al.Pd supported on alumina modified by phosphate: Highly phosphorus-resistant three-way catalyst for natural gas vehicles [J]. Journal of the Taiwan Institute of Chemical Engineers, 2020, 115: 108-16. [75]Chen J, Zhang G, Wu Y, et al.Pd Supported on Alumina Using CePO4 as an Additive: Phosphorus-Resistant Catalyst for Emission Control in Vehicles Fueled by Natural Gas[J].Industrial & Engineering Chemistry Research, 2020, 59(14):6497-505 [76]Hackleman B.Two-stroke Lean Burn Natural Gas Engine Oxidation Catalyst Degradation and Regeneration via Washing [D]; Colorado State University, 2018. [77]Cabello Galisteo F, Mariscal R, López Granados M, et al.Reactivation of a commercial diesel oxidation catalyst by acid washing[J].Environmental Science & Technology, 2005, 39(10):3844-8 [78]Christou S Y, G?sste J, Karlsson H L, et al.Regeneration of Aged Commercial Three-Way Catalytic Converters[J].Topics in Catalysis, 2009, 52(13-20):2029-34 [79]Christou S Y, Efstathiou A M.Efficient In-Situ Regeneration Method of the Catalytic Activity of Aged TWC[J].Topics in Catalysis, 2007, 42-43(1-4):415-9 [80]Subramanian B, Christou S Y, Efstathiou A M, et al.Regeneration of three-way automobile catalysts using biodegradable metal chelating agent-S,S-ethylenediamine disuccinic acid (S,S-EDDS)[J].Journal of Hazardous Materials, 2011, 186(2-3):999-1006 [81]Christou S Y, Efstathiou A M.Regeneration of Aged Commercial Three-Way Catalysts Using CI-Containing Reagents[J].Topics in Catalysis, 2013, 56(1-8):255-60 [82]Lambrou P S, Polychronopoulou K, Petallidou K C, et al.Oxy-chlorination as an effective treatment of aged Pd/CeO2-Al2O3 catalysts for Pd redispersion [J]. Applied Catalysis B: Environmental, 2012, 111-112: 349-59. [83]Lanzerath P, Guethenke A, Massner A, et al.Analytical investigations on ageing phenomena of catalytic exhaust gas aftertreatment components [J]. Catalysis Today, 2009, 147: S265-S70. [84]V?liheikki A, Kolli T, Honkanen M, et al.The Impact of Sulphur,Phosphorus and their Co-effect on PtSiO2–ZrO2 Diesel Oxidation Catalysts[J].Topics in Catalysis, 2016, 60(3-5):307-11 [85]Kanerva T, Honkanen M, Kolli T, et al.Microstructural Characteristics of Vehicle-Aged Heavy-Duty Diesel Oxidation Catalyst and Natural Gas Three-Way Catalyst[J].Catalysts, 2019, 9(2):137-