低温等离子体用于柴油机尾气脱硝的实验

doi:10.16085/j.issn.1000-6613.042

摘要/Abstract

摘要：

柴油机作为卡车、重型机械以及船舶的主动力装置仍被广泛采用，其尾气中氮氧化物的脱除技术也是目前的研究热点。本文搭建了模拟柴油机尾气的配气系统，采用介质阻挡放电产生低温等离子体（non-thermal plasma，NTP）的方法对模拟柴油机尾气进行了脱硝的实验研究。实验结果表明：针对本系统，电源效率和能量密度随着输入电压的增大而升高，当输入电压高于60V时，电源效率在90%以上；在O₂/N₂条件下，随着O₂浓度以及能量密度的增加，NO生成量逐渐增加，NO₂生成量先增加后降低最终趋于稳定；在NO/N₂条件下，低温等离子体对NO的脱除率接近100%；在NO/O₂/N₂条件下，随着NO浓度的增加，临界O₂浓度升高，O₂体积分数为1%时脱硝效率在90%以上，O₂体积分数高于14%时低温等离子体的脱硝率为负值，且随着能量密度的增加，生成的NO _x 浓度也更高，O₂浓度对低温等离子体的脱硝性能起决定性作用；在低能量密度时，加入NH₃会提高脱硝性能，高能量密度时NH₃会略微降低NTP的脱硝性能，当加入H₂O模拟真实柴油机尾气成分且喷氨时，获得的脱硝率最高为40.6%。

关键词: 柴油机尾气, 氮氧化物, 介质阻挡放电, 低温等离子体, 脱硝率

Abstract:

Diesel engines are still widely used as main power equipment for trucks, heavy machinery and ships. The technologies of nitrogen oxides removal from diesel exhaust are hot research topics. This paper sets up a gas supply system that simulates the diesel exhaust, and uses a dielectric barrier discharger (DBD) to generate non-thermal plasma (NTP) to investigate the removal of nitrogen oxides. The experimental results showed that the power efficiency and energy density increase with the input voltage for this system. The power efficiency is above 90% when the input voltage is higher than 60V. In the O₂/N₂ system, NO generation increases with the O₂ concentration and energy density, while NO₂ increases first, then decreases and stabilizes. The removal rate of NO is close to 100% by NTP in NO/N₂ system. For the NO/O₂/N₂ system, the critical O₂ concentration increases with NO concentration. With the increase of energy density, the denitrification efficiency is above 90% at 1% O₂ volume fraction and negative when O₂ volume fraction is higher than 14%. The O₂ concentration plays a decisive role in the denitration performance of the NTP. NH₃ improves the denitration rate at low energy density while slightly reduces the denitration rate at high energy density. The denitration rate is 40.6% at simulating real diesel exhaust conditions when H₂O and ammonia is added.

Key words: diesel exhaust, nitrogen oxides, dielectric barrier discharger, non-thermal plasma, denitration rate

中图分类号:

X511

汪宗御,邝海浪,张继锋,褚李林,纪玉龙. 低温等离子体用于柴油机尾气脱硝的实验[J]. 化工进展, 2019, 38(10): 4755-4766.

Zongyu WANG,Hailang KUANG,Jifeng ZHANG,Lilin CHU,Yulong JI. Experimental of diesel engine denitration by non-thermal plasma[J]. Chemical Industry and Engineering Progress, 2019, 38(10): 4755-4766.

图/表 15

图1 DBD脱硝实验系统

图2 DBD反应器结构及参数

图3 电源初始输出的正弦波（局部）

图4 电源输出的脉冲信号（2个周期）

图5 电压-电荷法求放电功率等效电路

图6 李萨如积分面积图

图7 1000μL·L-1 NO+1000μL·L-1 NH3+14%O2时电源能量密度和效率随输入电压的变化

图8 不同NO浓度时电源输出效率随输入电压的变化

图9 O2+N2条件下不同能量密度时NTP产生的影响 ·N +O2 → NO+·O (14)

图10 不同能量密度时NTP的脱硝性能（NO/N2）

图11 不同NO和O2条件下NTP的脱硝性能

图12 不同O2和NH3条件下，NTP的脱硝性能

图13 H2O对氮氧化物浓度的影响

图14 H2O和NH3对脱硝率的影响 e+H2O → e+·H+·OH (37)O(1D)+ H2O → ·OH+·OH (38)

图15 NO x 在NTP反应体系中的转化途径

参考文献 34

1	IMO. MEPC Resolution .203(62): Amendments to MARPOL Annex Ⅵ on Regulations for the Prevention of Air Pollution from Ships by Inclusion of New Regulations on Energy Efficiency for Ships [S]. 2011.
2	中华人民共和国环境保护部 . 非道路移动机械用柴油机排气污染物排放限值及测量方法(中国第三、四阶段) : GB 20891—2014 [S]. 北京: 中国环境科学出版社, 2014.
	Ministry of Environmental Protection of the People's Republic of China . Limits and measurement methods for exhaust pollutants from diesel engines of non-road mobile machinery (China Ⅲ, Ⅳ): GB 20891—2014 [S]. Beijing: China Environmental Science Press, 2016.
3	中华人民共和国环境保护部 . 船舶发动机排气污染物排放限值及测量方法(中国第一、二阶段): GB 15097—2016 [S]. 北京: 中国环境科学出版社, 2016.
	Ministry of Environmental Protection of the People 's Republic of China . Limits and measurement methods for emission of marine engine exhaust pollutants (China Ⅰ, Ⅱ): GB 15097—2016 [S]. Beijing: China Environmental Science Press, 2016.
4	DI NATALE F , CAROTENUTO C , D'ADDIO L , et al . New technologies for marine diesel engine emission control [J]. Chemical Engineering Transactions, 2013, 32: 361-366.
5	方平, 陈雄波, 唐子君, 等 . 船舶柴油机大气污染物排放特性及控制技术研究现状 [J]. 化工进展, 2017, 36(3): 1067-1076.
	FANG Ping , CHEN Xiongbo , TANG Zijun , et al . Current research status on air pollutant emission characteristics and control technology of marine diesel engine [J]. Chemical Industry and Engineering Progress, 2017, 36(3): 1067-1076.
6	MA Siming , ZHAO Yongchun , YANG Jianping , et al . Research progress of pollutants removal from coal-fired flue gas using non-thermal plasma [J]. Renewable and Sustainable Energy Reviews, 2017, 67: 791-810.
7	PATIL B S , CHERKASOV N , LANG J , et al . Low temperature plasma-catalytic NO _x synthesis in a packed DBD reactor: effect of support materials and supported active metal oxides [J]. Applied Catalysis B: Environmental, 2016, 194: 123-133.
8	BALACHANDRAN W , MANIVANNAN N , BELECA R , et al . Nonthermal plasma system for marine diesel engine emission control [J]. IEEE Transactions on Industry Applications, 2016, 52(3): 2496-2505.
9	KUWAHARA T , NAKAGUCHI H , KUROKI T , et al . Continuous reduction of cyclic adsorbed and desorbed NO _x in diesel emission using nonthermal plasma [J]. Journal of Hazardous Materials, 2016, 308: 216-224.
10	ZHANG Zhaoshun , CROCKER M , YU Limei , et al . Non-thermal plasma assisted NO _x storage and reduction over a cobalt-containing Pd catalyst using H₂ and/or CO as reductants [J]. Catalysis Today, 2015, 258: 175-182.
11	GUO Lifang , SHU Youju , GAO Junmin . Present and future development of flue gas control technology of DeNO _x in the World [J]. Energy Procedia, 2012, 17: 397-403.
12	刘文正, 赵帅, 柴茂林, 等 . 采用辉光放电等离子体的烟气处理技术研究[J]. 中国环境科学, 2017(8): 2905-2914.
	LIU Wenzheng , ZHAO Shuai , CHAI Maolin , et al . Technology of flue gas treatment with glow discharge plasma [J]. China Environmental Science, 2017(8): 2905-2914.
13	DING Shuilan , YU Qi , ZHANG Yingzhou , et al . Experimental study on NO removal using non-thermal plasma oxidation alkali absorption [J]. Journal of Advanced Oxidation Technologies, 2015, 18(1): 114-122.
14	WANG Tao , SUN Baomin , XIAO Haiping , et al . Effect of reactor structure in DBD for nonthermal plasma processing of NO in N₂ at ambient temperature [J]. Plasma Chemistry and Plasma Processing, 2012, 32(6): 1189-1201.
15	YUKIMURA K , KAWAMURA K , HIRAMATSU T , et al . Efficient decomposition of NO by ammonia radical-injection method using an intermittent dielectric barrier discharge [J]. Thin Solid Films, 2007, 515(9): 4278-4282.
16	李斌 . 船舶柴油机[M]. 大连: 大连海事大学出版社, 2008.
	LI Bin . Marine diesel engine [M]. Dalian: Dalian Maritime University Press, 2008.
17	CHMIELEWSKI A G , ZWOLINSKA E , LICKI J , et al . A hybrid plasma-chemical system for high-NO _x flue gas treatment [J]. Radiation Physics and Chemistry, 2018, 144: 1-7.
18	YU Qingjun , GAO Yueming , TANG Xiaolong , et al . Removal of NO from flue gas over HZSM-5 by a cycling adsorption-plasma process [J]. Catalysis Communications, 2018, 110: 18-22.
19	ZHAO Guibing , GARIKIPATI S V B J , HU Xudong , et al . Effect of oxygen on nonthermal plasma reactions of nitrogen oxides in nitrogen [J]. AIChE Journal, 2005, 51(6): 1800-1812.
20	周莹, 仲兆平, 付宗明, 等 . 等离子体氧化NO的试验研究及神经网络预测[J]. 华东电力, 2012(7): 1217-1221.
	ZHOU Ying , ZHONG Zhaoping , FU Zongming , et al . Experimental research and neural network prediction of NO oxidation based on plasma [J]. East China Electric Power, 2012(7): 1217-1221.
21	张居兵, 周莹, 仲兆平, 等 . 等离子体氧化NO耦合湿式氨法同时脱硫脱硝试验研究[J]. 东南大学学报(自然科学版), 2014(6): 1194-1199.
	ZHANG Jubing , ZHOU Ying , ZHONG Zhaoping , et al . Experimental study on simultaneous desulfurization and denitrification with ammonia in WFGD system combined with plasma oxidation of NO [J]. Journal of Southeast University (Natural Science Edition), 2014(6): 1194-1199.
22	ARITOSHI K , FUJIWARA M , ISHIDA M . Production and removal mechanisms of discharge NO _x treatment in N₂/O₂ gas mixture [J]. Japanese Journal of Applied Physics, 2002, 41(6R): 3936.
23	MOK Y S, NAM I . Modeling of pulsed corona discharge process for the removal of nitric oxide and sulfur dioxide [J]. Chemical Engineering Journal, 2002, 85(1): 87-97.
24	ROSENTHAL L A , DAVIS D A . Electrical characterization of a corona discharge for surface treatment [J]. IEEE Transactions on Industry Application, 1975, 11(3): 328-335.
25	王东 . 介质阻挡放电等离子体脱除氮氧化物的实验研究[D]. 北京: 华北电力大学, 2014.
	WANG Dong . Experimental research on the removal of nitrogen oxides by dielectric barrier discharge plasma [D]. Beijing: North China Electric Power University, 2014.
26	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, 2009.
	SUN Honghua . Study on the removal of SO₂/NO with dielectric barrier discharge non-thermal plasma [D]. Beijing: North China Electric Power University, 2009.
27	张晓星, 胡雄雄, 肖焓艳, 等 . 不同背景气体对介质阻挡放电降解SF₆气体影响的实验研究[J]. 中国电机工程学报, 2018, 38(3): 937-946.
	ZHANG Xiaoxing , HU Xiongxiong , XIAO Hanyan , et al . Experimental study on the effect of different dilution gases to the degradation of SF₆ gas by dielectric barrier discharge [J]. Proceedings of the CSEE, 2018,38(3): 937-946.
28	HERRON J . Evaluated chemical kinetics data for reactions of N(²D), N(²P), and N₂(A³∑_u ⁺) in the gas phase [J]. Journal of Physical and Chemical Reference Data, 1999, 28: 1453-1483.
29	FERNANDEZ A , GOUMRI A , FONTIJN A . Kinetics of the reactions of N(4S) atoms with O₂ and CO₂ over wide temperatures ranges [J]. The Journal of Physical Chemistry A, 1998, 102(1): 168-172.
30	HERRON J T , GREEN D S . Chemical kinetics database and predictive schemes for nonthermal humid air plasma chemistry. Part Ⅱ. Neutral species reactions [J]. Plasma Chemistry and Plasma Processing, 2001, 21(3): 459-481.
31	ATKINSON R , BAULCH D L , COX R A, et al . Evaluated kinetic and photochemical data for atmospheric chemistry: Supplement Ⅳ IUPAC subcommittee on gas kinetic data evaluation for atmospheric chemistry [J]. Journal of Physical and Chemical Reference Data, 1992, 21(6): 1125-1568.
32	纪瑞军, 徐文青, 王健, 等 . 臭氧氧化脱硝技术研究进展[J]. 化工学报, 2018, 69(6): 2353-2363.
	JI Ruijun , XU Wenqing , WANG Jian , et al . Research progress of ozone oxidation denitrification technology [J]. CIESC Journal, 2018, 69(6): 2353-2363.
33	梁文俊, 李晶欣, 竹涛 . 低温等离子体大气污染控制技术及应用[M]. 北京: 化学工业出版社, 2016.
	LIANG Wenjun , LI Jingxin , ZHU Tao . Air pollution control technology and application of low temperature plasma [M]. Beijing: Chemical Industry Press, 2016.
34	TOKUNAGA O , SUZUKI N . Radiation chemical reactions in NO _x and SO₂ removals from flue gas [J]. Radiation Physics and Chemistry, 1984, 24(1): 145-165.

编辑推荐

Metrics

阅读次数

全文

225

HTML			PDF

最新录用	在线预览	正式出版	最新录用	在线预览	正式出版
0	0	7	0	0	218

来源	本网站	其他网站

次数	86	139
比例	38%	62%

摘要

335

最新录用	在线预览	正式出版

0	0	335

来源	本网站	其他网站

次数	221	115
比例	66%	34%

[1]	赖诗妮, 江丽霞, 李军, 黄宏宇, 小林敬幸. 含碳掺氨燃料的研究进展[J]. 化工进展, 2023, 42(9): 4603-4615.
[2]	李佳, 樊星, 陈莉, 李坚. 硝酸生产尾气中NO _x 和N₂O联合脱除技术研究进展[J]. 化工进展, 2023, 42(7): 3770-3779.
[3]	龙红明, 丁龙, 钱立新, 春铁军, 张洪亮, 余正伟. 烧结烟气中NO _x 和二英的减排现状及发展趋势[J]. 化工进展, 2022, 41(7): 3865-3876.
[4]	杨希刚, 陈国庆, 黄林滨, 古世军, 李昌松, 张勇, 金保昇. 尿素法SNCR对大型电站煤粉锅炉运行影响的工业试验[J]. 化工进展, 2022, 41(7): 3573-3581.
[5]	韩徳琳, 李丹, 王天天, 张海, 张扬, 王随林. 位移钝体稳燃的旋流预混燃烧污染物生成特性[J]. 化工进展, 2022, 41(6): 2915-2923.
[6]	王新宇, 黄亚继, 徐力刚, 李志远, 李偲, 刘晓东. 调节同层二次风以缓解双切圆锅炉高温腐蚀的数值模拟[J]. 化工进展, 2022, 41(5): 2292-2300.
[7]	王思怡, 李月慧, 葛玉洁, 王焕然, 赵璐璐, 李先春. NTP-DBD气化城市污泥及其模型化合物：气氛对产物分布及特性的影响[J]. 化工进展, 2022, 41(4): 2150-2160.
[8]	张维, 汪宗御, 郭玉, 杨孟飞, 李政楷, 常超, 张继锋, 纪玉龙. 大气压介质阻挡放电及协同催化剂脱硝研究进展[J]. 化工进展, 2022, 41(12): 6644-6655.
[9]	杨景瑞, 王莹, 陈虎, 吕永康. 氧浓度对调节NO _x 氧化度协同CABR法脱硝性能及菌群结构的影响[J]. 化工进展, 2022, 41(11): 6139-6148.
[10]	谭潇, 齐随涛, 周一鸣, 石利斌, 程光旭, 伊春海, 杨伯伦. 非热等离子体协同锰铁双金属催化剂直接催化还原NO[J]. 化工进展, 2022, 41(11): 5850-5857.
[11]	毕文菲, 代成义, 李雪梅, 贺建勋, 赵彬然, 马晓迅. 等离子体与Cu-Pd/S-1催化剂协同催化甲烷转化制低碳烯烃[J]. 化工进展, 2022, 41(1): 227-236.
[12]	彭冲, 刘鹏, 胡永康, 肖文德, 潘云翔. 低温等离子体构筑高效Ni基催化剂进展[J]. 化工进展, 2021, 40(7): 3553-3563.
[13]	尹子骏, 苏胜, 王中辉, 王乐乐, 安晓雪, 赵志刚, 陈逸峰, 刘涛, 汪一, 胡松, 向军. 燃煤烟气中SO₃与NH₄HSO₄生成特性及其控制方法研究进展[J]. 化工进展, 2021, 40(4): 2328-2337.
[14]	刘月华, 上官炬, 刘守军, 杨颂, 杜文广. 铁镍复合助剂对煤热解过程中氮迁移规律的影响[J]. 化工进展, 2021, 40(1): 164-172.
[15]	赵亚飞, 叶凯, 庄烨, 郑进保. 锰基催化剂协同等离子降解VOCs研究进展[J]. 化工进展, 2020, 39(S2): 175-184.