低温等离子体辅助燃烧降低烟气中 NO_x 和二英排放的研究进展

Research Advances in NO_x and Dioxins’ Mitigation in Flue Gas by Non-Thermal Plasma Assisted Combustion

摘要

本文归纳了多种 NTP 辅助燃烧方式对燃烧进程、污染物排放影响方面的研究进展,重点关注其对 NO_x 和二英排放的影响．首先介绍了 NTP 形成的自由基对燃烧进程的影响机制；其次,分析了 NTP 的应用及其电压、功率等参数对气、固、液相燃料燃烧 NO_x 排放的影响及反应动力学机理；第三,总结了 NTP 产生的 OH、H、O 等自由基对固废燃烧过程中特有污染物二英及其前驱体的降解机理；最后,讨论了 NTP 对点火燃烧过程中点火延迟时间和燃烧效率的影响．总体上,NTP 辅助燃烧作为一种极具前途的技术,将在提高固废燃烧效率、有效降低 NO_x 和二英等污染物排放方面发挥重要作用．

Abstract

This paper reviews research advances in pollutant emissions control via various NTP-assisted approaches during combustion,with a particular focus on their impacts on NO_x and dioxin mitigation. Firstly,the mechanism by which radicals(e.g.,O,H,OH)generated by NTP influence the combustion process is introduced. Secondly,the application of NTP technology in gaseous,solid,and liquid fuel combustion is analyzed,along with the effects of parameters such as voltage and power on NO_x emissions and the associated reaction kinetics mechanisms. Thirdly,the degradation mechanisms of dioxins and their precursors during solid waste combustion,mediated by radicals such as OH,H,and O generated by NTP,are summarized. Finally,the effects of NTP on ignition delay time and combustion efficiency during ignition and combustion are discussed. In general,NTP-assisted combustion is a highly promising technology,and it will play a significant role in enhancing the solid wastes’ combustion efficiency and reducing emissions of pollutants such as NO_x and dioxins.

关键词

低温等离子体(NTP) / 辅助燃烧 / 自由基 / NO_x / 二英

Key words

non-thermal plasma(NTP) / assisted combustion / free radicals / NO_x / dioxins

参考文献

[1] Elkaee S, Phule A D, Yang J H. Advancements in(SCR)technologies for NO_x reduction:A comprehensive review of reducing agents [J]. Process Safety and Environmental Protection, 2024, 184: 854-880.

[2] Gomez E, Rani D A, Cheeseman C R, et al. Thermal plasma technology for the treatment of wastes:A critical review[J]. Journal of Hazardous Materials, 2009, 161(2—3): 614-626.

[3] Ju Y, Sun W. Plasma assisted combustion:Dynamics and chemistry[J]. Progress in Energy and Combustion Science, 2015, 48: 21-83.

[4] Mu Y, Khatibi M, Williams P T. Non—thermal plasma(NTP)assisted removal of dioxins and furans in municipal solid waste incineration(MSWI)fly ash over pt/ZSM—5 catalyst[J]. Journal of Environmental Chemical Engineering, 2025, 13(3): 117121.

[5] 贺靖龙,洪 鎏, 周洪权, 等. NTP 活化助燃空气降低垃圾焚烧中 NO_x 排放研究 [J]. 燃烧科学与技术, 2023, 29(1): 85-93.

[6] He Jinglong, Hong Liu, Zhou Hongquan, et al. Investigation on De—NO_x effect in municipal solid waste incineration process by supplying NTP activated combustion air [J]. Journal of Combustion Science and Technology, 2023, 29(1): 85-93(in Chinese).

[7] Mutaf—Yardimci O, Saveliev A V, Fridman A A, et al. Thermal and nonthermal regimes of gliding arc discharge in air flow[J]. Journal of Applied Physics, 2000, 87(4): 1632-1641.

[8] 郭 彬. 介质阻挡放电低温等离子体脱硝性能研究与能耗分析[D]. 济南: 山东大学, 2018.

[9] Guo Bin. Performance Research and Energy Consumption Analysis of NO—Removal by Dielectric Barrier Discharge Non—Thermal Plasma[D]. Jinan: Shandong University, 2018(in Chinese).

[10] 鲁 娜, 孙丹凤,王 冰, 等. 交流旋转滑动弧的放电特性[J]. 高电压技术, 2018, 44(6): 1930-1937.

[11] Lu Na, Sun Danfeng, Wang Bing, et al. Discharge characteristic of AC rotating gliding arc[J]. High Voltage Engineering, 2018, 44(6): 1930-1937(in Chinese).

[12] 孙红华. 介质阻挡放电低温等离子体脱硫脱硝研究[D]. 北京: 华北电力大学(北京), 2009.

[13] Sun Honghua. Study on the Removal of SO₂/NO with Dielectric Barrier Discharge Non—Thermal Plasma [D]. Beijing: North China Electric Power University(Beijing), 2009(in Chinese).

[14] Okafor E C, Somarathne K D K A, Hayakawa A, et al. Towards the development of an efficient low—NO_x ammonia combustor for a micro gas turbine [J]. Proceedings of the Combustion Institute, 2019, 37(4): 4597-4606.

[15] Ju R, Wang J, Zhang M, et al. Stability and emission characteristics of ammonia/air premixed swirling flames with rotating gliding arc discharge plasma[J]. Energy, 2023, 277: 127649.

[16] Shahsavari M, Konnov A A, Bai X S, et al. Synergistic effects of nanosecond plasma discharge and hydrogen on ammonia combustion[J]. Fuel, 2023, 348: 128475.

[17] Kim G T, Park J, Chung S H, et al. Effects of non—thermal plasma on turbulent premixed flames of ammonia/air in a swirl combustor[J]. Fuel, 2022, 323: 124227.

[18] Choe J, Sun W. Plasma assisted ammonia combustion:enhanced flame stability and reduced NO_x emission [C]// AIAA Scitech 2022 Forum. San Diego,CA:American Institute of Aeronautics and Astronautics, 2022,AIAA 2022—1452.

[19] 陈 磊. 介质阻挡放电辅助氨/空气预混燃烧[D]. 合肥: 安徽大学, 2023.

[20] Chen Lei. Ammonia/Air Premixed Combustion Assisted by Dielectric Barrier Discharge[D]. Hefei: Anhui University, 2023(in Chinese).

[21] Fan Y, Zhu T, Li Z, et al. Non—equilibrium plasma cracking assisted ammonia marine engine for zero carbon emissions[J]. International Journal of Hydrogen Energy, 2025, 112: 433-445.

[22] Lin Q, Jiang Y, Liu C, et al. Controllable NO emission and high flame performance of ammonia combustion assisted by non—equilibrium plasma[J]. Fuel, 2022, 319: 123818.

[23] Rekkas—Ventiris G, Sabia P, Sorrentino G, et al. Nanosecond pulsed plasma—assisted MILD combustion of ammonia[J]. Proceedings of the Combustion Institute, 2024, 40(1—4): 105384.

[24] Deng K, He A, Ye S, et al. Addressing NO_x formation mechanisms of NH₃/H₂ dual—fuel flame under DBD plasma—assisted combustion resolved by intermediate radicals analysis [J]. International Journal of Hydrogen Energy, 2024, 96: 938-951.

[25] Ju R, Wang J, Zhang M, et al. Experimental study on burning velocity,structure,and NO_x emission of premixed laminar and swirl NH₃/H₂/air flames assisted by non—thermal plasma [J]. Applications in Energy and Combustion Science, 2023, 14: 100149.

[26] 李双龙, 顾明言,位 鑫, 等. 等离子体辅助氨煤混燃过程 NO_x 排放特性研究 [J]. 煤炭转化, 2025, 48(2): 92-100.

[27] Li Shuanglong, Gu Mingyan, Wei Xin, et al. Study on NO_x emission characteristics during plasma—assisted ammonia—coal co—combustion process [J]. Coal Conversion, 2025, 48(2): 92-100(in Chinese).

[28] 孙锦国,黄 骞, 张易阳, 等. 滑动弧辅助甲烷/氨旋流火焰的稳燃和排放特性[J]. 工程热物理学报, 2022, 43(8): 2234-2241.

[29] Sun Jinguo, Huang Qian, Zhang Yiyang, et al. Stabilization and NO_x emission of gliding arc—assisted CH₄/NH₃ swirl flames [J]. Journal of Engineering Thermophysics, 2022, 43(8): 2234-2241(in Chinese).

[30] Zhang X, Moosakutty S P, Rajan R P, et al. Combustion chemistry of ammonia/hydrogen mixtures:Jet—stirred reactor measurements and comprehensive kinetic modeling[J]. Combustion and Flame, 2021, 234: 111653.

[31] Shioyoke A, Hayashi J, Murai R, et al. Numerical investigation on effects of nonequilibrium plasmaon laminar burning velocity of ammonia flame[J]. Energy & Fuels, 2018, 32(3): 3824-3832.

[32] Valera—Medina A, Xiao H, Owen—Jones M, et al. Ammonia for power[J]. Progress in Energy and Combustion Science, 2018, 69: 63-102.

[33] Tang H, Gubbi S, Sun W. Investigation of flame structure in plasma—assisted ammonia swirling flames using NH planar laser—induced fluorescence[J]. Combustion and Flame, 2025, 274: 114006.

[34] Hayakawa A, Arakawa Y, Mimoto R, et al. Experimental investigation of stabilization and emission characteristics of ammonia/air premixed flames in a swirl combustor[J]. International Journal of Hydrogen Energy, 2017, 42(19): 14010-14018.

[35] Choe J, Sun W. Experimental investigation of non—equilibrium plasma—assisted ammonia flames using * 2 NH chemiluminescence and OH planar laser—induced fluorescence[J]. Proceedings of the Combustion Institute, 2023, 39(4): 5439-5446.

[36] Taneja T S, Johnson P N, Yang S. Nanosecond pulsed plasma assisted combustion of ammonia—air mixtures:Effects on ignition delays and NO_x emission [J]. Combustion and Flame, 2022, 245: 112327.

[37] Kim G T, Seo B H, Lee W J, et al. Effects of applying non—thermal plasma on combustion stability and emissions of NO_x and CO in a model gas turbine combustor [J]. Fuel, 2017, 194: 321-328.

[38] Varella R A, Sagás J C, Martins C A. Effects of plasma assisted combustion on pollutant emissions of a premixed flame of natural gas and air[J]. Fuel, 2016, 184: 269-276.

[39] Paulauskas R, Martuzevičius D, Patel R B, et al. Biogas combustion with various oxidizers in a nanosecond DBD microplasma burner[J]. Experimental Thermal and Fluid Science, 2020, 118: 110166.

[40] Ghabi A, Boushaki T, Bocanegra P E, et al. Laminar burning velocity,adiabatic flame temperature,and pollutants of biogas/air mixture at various CO₂ concentrations and plasma assist [J]. Combustion Science and Technology, 2023, 195(7): 1599-1621.

[41] Perrin—Terrin J B, Vaysse N, Durox D, et al. Plasma—assisted combustion of hydrogen swirling flames:Extension of lean blowout limit and NO_x emissions [J]. Proceedings of the Combustion Institute, 2024, 40(1—4): 105546.

[42] Liu X, He L, Zeng H, et al. Emission characteristics of kerosene—air spray combustion with plasma assistance[J]. AIP Advances, 2015, 5(9): 097180.

[43] Liu X, He L, Yi C, et al. Emission characteristics of aviation kerosene combustion in aero—engine annular combustor with low temperature plasma assistance[J]. Thermal Science, 2019, 23(2A): 647-660.

[44] Lin Y C, Yang P M, Chen C B. Reducing emissions of polycyclic aromatic hydrocarbons and greenhouse gases from engines using a novel plasma—enhanced combustion system[J]. Aerosol and Air Quality Research, 2013, 13(3): 1107-1115.

[45] Chen H H, Wu C Y. Experimental investigation of the plasma—assisted spray combustion of methanol/water mixtures[J]. Fuel, 2024, 363: 130972.

[46] 贺靖龙. NTP 活化空气助燃垃圾焚烧的燃烧特性和 NO_x 减排特性研究 [D]. 上海: 同济大学. 2022.

[47] He Jinglong. Study on the Combustion Characteristics and De—NO_x Behaviors by Using NTP Activated Air for Waste Incineration [D]. Shanghai: Tongji University, 2002(in Chinese).

[48] Liang W J, Yin G B, Shi X J, et al. Performance of the chlorobenzene destruction with nonthermal plasma:Effects of the gas conditions and the gas components[J]. Journal of Environmental Engineering, 2023, 149(4): 04023009.

[49] Zhu T, Zhang X, Ma M, et al. 1,2,4—trichlorobenzene decomposition using non—thermal plasma technology[J]. Plasma Science and Technology, 2020, 22(3): 034011.

[50] 徐 飞, 骆仲泱,王 鹏, 等. 脉冲放电降解垃圾焚烧飞灰 PAHs 和二恶英的研究[J]. 中国电机工程学报, 2007, 27(32): 34-39.

[51] Xu Fei, Luo Zhongyang, Wang Peng, et al. Study on simultaneous decomposition of PAHs and dioxins in municipal solid waste fly ashes by pulse corona discharge[J]. Proceedings of the CSEE, 2007, 27(32): 34-39(in Chinese).

[52] Sidhu S, Edwards P. Role of phenoxy radicals in PCDD/F formation[J]. International Journal of Chemical Kinetics, 2002, 34(9): 531-541.

[53] Xu F, Wang H, Zhang Q, et al. Kinetic properties for the complete series reactions of chlorophenols with oh radicals—relevance for dioxin formation[J]. Environmental Science & Technology, 2010, 44(4): 1399-1404.

[54] Yu X, Dang X, Li S, et al. Abatement of chlorobenzene by plasma catalysis:Parameters optimization through response surface methodology(RSM),degradation mechanism and PCDD/Fs formation[J]. Chemosphere, 2022, 298: 134274.

[55] 杜蒙蒙, 温正城,李 源, 等. OH 自由基降解二英 OCDD 的反应机理及动力学研究[J]. 环境科学学报, 2018, 38(3): 961-967.

[56] Du Mengmeng, Wen Zhengcheng, Li Yuan, et al. Mechanism and kinetic study on the destruction of OCDD by OH radical[J]. Acta Scientiae Circumstantiae, 2018, 38(3): 961-967(in Chinese).

[57] Gong C, Sun X, Zhang C, et al. Theoretical study on the degradation reaction of octachlorinated dibenzo—p—dioxin with atomic oxygen O(³P)in dielectric barrier discharge reactor [J]. Journal of Environmental Sciences, 2014, 26(11): 2283-2289.

[58] Wen Z, Wang Z, Xu J, et al. Quantum chemistry study on the destruction mechanism of 2,3,7,8—TCDD by OH and O₃ radicals [J]. Chemosphere, 2013, 92(3): 293-298.

[59] 王 静. PCDD/Fs 热力学相关性质及其与 H 自由基作用机制的理论研究[D]. 曲阜: 曲阜师范大学, 2013.

[60] Wang Jing. Theoretical Study on Thermodynamic Properties of PCDD/Fs and Their Interaction Mechanism with H Radicals[D]. Qufu: Qufu Normal University, 2013(in Chinese).

[61] Zhang C, Sun T, Sun X. Mechanism for OH—initiated degradation of 2,3,7,8—tetrachlorinated dibenzo—p—dioxins in the presence of O₂ and NO/H₂O [J]. Environmental Science & Technology, 2011, 45(11): 4756-4762.

[62] 陈宋璇,王 昊, 张东伟, 等. 垃圾焚烧飞灰中 2,3,7,8—TCDF 低温降解反应模拟研究[J]. 中国有色冶金, 2025, 54(4): 139-146.

[63] Chen Songxuan, Wang Hao, Zhang Dongwei, et al. Simulation investigation on low temperature degradation reaction of 2,3,7,8—TCDF in fly ash[J]. China Non—ferrous Metallurgy, 2025, 54(4): 139-146(in Chinese).

[64] 张 坤, 孙胜敏 ,张 辉. OH 自由基引发的 2,3,7,8—四氯代二苯并呋喃降解机理的理论研究[J]. 东北师大学报(自然科学版), 2014, 46(4): 103-109.

[65] Zhang Kun, Sun Shengmin, Zhang Hui. The mechanism study of the degradation reaction of 2,3,7,8—TCDF initiated by OH radical[J]. Journal of Northeast Normal University(Natural Science Edition), 2014, 46(4): 103-109(in Chinese).

[66] Sun X, Zhang C, Zhao Y, et al. Atmospheric chemical reactions of 2,3,7,8—tetrachlorinated dibenzofuran initiated by an OH radical:Mechanism and kinetics study[J]. Environmental Science & Technology, 2012, 46(15): 8148-8155.

[67] 张 辉, 孙胜敏. OH 自由基引发的 2,3,7,8—TCDF 环异构化的反应机理[J]. 中国科技论文, 2016, 11(12): 1422-1425.

[68] Zhang Hui, Sun Shengmin. Reaction mechanism of ring isomerization of 2,3,7,8—TCDF initiated by OH radical[J]. China Sciencepaper, 2016, 11(12): 1422-1425(in Chinese).

[69] Lee J E, Choi W, Mhin B J, et al. Theoretical study on the reaction of OH radicals with polychlorinated dibenzo—p—dioxins[J]. The Journal of Physical Chemistry A, 2004, 108(4): 607-614.

[70] Wang S, Yu J, Cheng W, et al. Chemical kinetic analysis of plasma excited methane combustion[J]. Chemical Physics Letters, 2019, 730: 399-406.

[71] Zhang L, Yu J, Cheng W, et al. Study on ignition characteristics of kerosene pre—combustion plasma jet igniter[J]. Physics of Fluids, 2024, 36(6): 065130.

[72] Zhang P, Zhong W, Li Q, et al. Effect of plasma on combustion characteristics of boron[J]. Chinese Physics B, 2017, 26(11): 110501.

[73] Gong C, Yi L, Wang K, et al. Numerical modeling of plasma—assisted combustion effects on firing and intermediates in the combustion process of methanol—air mixtures[J]. Energy, 2020, 192: 116598.

[74] Zhang M, Chen Q, Liu N, et al. Kinetic insights into ammonia—hydrogen doped ignition and emission assisted by nanosecond pulsed discharge[J]. International Journal of Hydrogen Energy, 2024, 78: 773-782.

[75] Pastor J V, García—Oliver J M, García A, et al. Combustion improvement and pollutants reduction with diesel—gasoline blends by means of a highly tunable laser plasma induced ignition system[J]. Journal of Cleaner Production, 2020, 271: 122499.

[76] Hwang J, Kim W, Bae C. Influence of plasma—assisted ignition on flame propagation and performance in a spark—ignition engine[J]. Applications in Energy and Combustion Science, 2021, 6: 100029.

[77] Fei L, Zhao B B, Chen Y, et al. Rotating gliding arc discharge plasma—assisted combustion from ignition hole[J]. Experimental Thermal and Fluid Science, 2021, 129: 110473.

[78] Chen Y, He L M, Fei L, et al. Experimental study of dielectric barrier discharge plasma—assisted combustion in an aero—engine combustor[J]. Aerospace Science and Technology, 2020, 99: 105765.

基金资助

上海市科学技术委员会碳达峰碳中和专项资助项目(22dz1208200)

上海市固体废物处理与回收工程研究中心开放基金资助项目(2021GFZX008)