Abstract：This paper mainly discusses the research progress of chemical warfare agents (CWAs) decontamination by low temperature plasma technology. The classification and toxicity of CWAs were reviewed. The advantages and disadvantages, current developing trend and feasibility of traditional decontamination technology and catalyst decontamination were analyzed. Besides, low temperature plasma technology was introduced for CWAs degradation. The application of different plasma discharges including plasma jet, dielectric barrier discharge and microwave plasma for CWAs degradation were reviewed. The type of CWAs, reaction conditions and degradation efficiency in a plasma-CWAs degradation system were well analyzed. In addition, the synergetic effect between plasma and catalyst for CWAs degradation was proposed and CWAs degradation mechanism was discussed. Finally, the main problem for large industrial application of plasma CWAs degradation technology was analyzed. This research has significant reference value for promoting the application of low temperature plasma for CWAs degradation.
王瑞雪, 李忠文, 虎攀, 杨亚文, 夏章川. 低温等离子体化学毒剂洗消技术研究进展[J]. 电工技术学报, 2021, 36(13): 2767-2781.
Wang Ruixue, Li Zhongwen, Hu Pan, Yang Yawen, Xia Zhangchuan. Review of Research Progress of Plasma Chemical Warfare Agents Degradation. Transactions of China Electrotechnical Society, 2021, 36(13): 2767-2781.
[1] Hatfill S J.Chemical warfare: nerve agents[J]. Journal of American Physicians and Surgeons, 2019, 24(1): 19-24. [2] Barranco V P.Mustard gas and the dermatologist[J]. International Journal of Dermatology, 1991, 30(10): 684-686. [3] Picard B, Chataigner I, Maddaluno J, et al.Introduction to chemical warfare agents, relevant simulants and modern neutralisation methods[J]. Organic & Biomolecular Chemistry, 2019, 17: 6528-6537. [4] 沈忠, 钟近艺, 郑禾, 等. 光催化技术在化学毒剂洗消领域的研究进展[J]. 环境科学与技术, 2015, 38(11): 14-20. Shen Zhong, Zhong Jinyi, Zheng He, et al.Research progress of photocatalytic technology in the field of chemical agent decontamination[J]. Environmental Science and Technology, 2015, 38(11): 14-20. [5] Gupta A K, Dubey D K, Kaushik M P.A simple and economical chemical neutralization method for the destruction of sulfur mustard and its analogues[J]. Journal of Hazardous Materials, 2007, 139(1): 154-159. [6] 白雪莲, 穆中国. 化学战剂消毒剂的研究现状及其发展趋势[J]. 辽宁化工, 2019(5): 421-422. Bai Xuelian, Mu Zhongguo.Research status and development trend of chemical warfare agent disinfectant[J]. Liaoning Chemical Industry, 2019(5): 421-422. [7] Saxena A, Srivastava A K, Singh B, et al. Removal of sulphur mustard, sarin and simulants on impregnated silica nanoparticles[J]. Journal of Hazardous Materials, 2011, 211-212(2): 226-232. [8] 沈忠, 钟近艺, 王泠沄, 等. 锆掺杂二氧化钛光催化降解2-CEES和DMMP的原位红外与固体核磁研究[J]. 分子催化, 2016, 30(3): 260-268. Shen Zhong, Zhong Jinyi, Wang Lingyun, et al.In situ FTIR and solid state NMR studies on the photocatalytic degradation of 2-CEES and DMMP by zirconium doped titanium dioxide[J]. Molecular Catalysis, 2016, 30(3):260-268. [9] Steng V, Grygar T M, Oplustil F, et al.Sulphur mustard degradation on zirconium doped Ti-Fe oxides[J]. Journal of Hazardous Materials, 2011, 192(3):1491-1504. [10] Mahato T H, Singh B, Srivastava A K, et al.Effect of calcinations temperature of CuO nanoparticleon the kinetics of decontamination and decontamination products of sulphur mustard[J]. Journal of Hazardous Materials, 20l1, 192(3): 1890-1895. [11] Gopinath A, Krishna K.Photocatalytic degradation of a chlorinated organic chemical using activated carbon fiber coupled with semiconductor[J]. Photochemistry & Photobiology, 2019, 95(6): 1311-1319. [12] Jay L, Chirwa E M N, Tichapondwa S M. The effect of reaction conditions on the degradation of phenol by UV/TiO2 photocatalysis[J]. Chemical Engineering Transactions, 2019, 76: 1375-1380. [13] Lee M S, Garibay S J, Ploskonka A M, et al.Bioderived protoporphyrin IX incorporation into a metal-organic framework for enhanced photocatalytic degradation of chemical warfare agents[J]. MRS Communications, 2019, 9(2): 464-473. [14] 慈颖, 王思, 张晓龙, 等. 铁铜共掺杂纳米二氧化钛用于降解化学毒剂的性能研究[J]. 中国国境卫生检疫杂志, 2019, 42(2): 116-120. Ci Ying, Wang Si, Zhang Xiaolong, et al.Chemical warfare agents degradation on Fe-Cu codoped TiO2 nanoparticles[J]. Chinese Journal of Frontier Health and Quarantine, 2019, 42(2): 116-120. [15] Yang Y, Baker J A, Ward J R,et al.Decontamination of chemical warfare agents[J]. Chemical Reviews, 1992, 92(8): 1729-1743. [16] Liang Huixin, Yao Aonan, Jiao Xiuling, et al.Fast and sustained degradation of chemical warfare agent simulants using flexible self-supported metal-organic-framework filters[J]. ACS Applied Materials & Interfaces, 2018, 10(24): 20396-20403. [17] Mondloch J E, Katz M J, Iii W C I, et al. Destruction of chemical warfare agents using metal-organic frameworks[J]. Nature Materials, 2015, 14(5): 512-516. [18] Koning M C D, Peterson G W, Grol M V, et al. Degradation and detection of the nerve agent VX by a chromophore-functionalized zirconium MOF[J]. Chemistry of Materials, 2019, 31(18): 7417-7424. [19] Wang S, Bromberg L, Schreuder-Gibson H, et al.Organophophorous ester degradation by chromium (III) terephthalate metal-organic framework (MIL-101) chelated to N, N-dimethylaminopyridine and related aminopyridines[J]. ACS Applied Materials & Interfaces, 2013, 5(4): 1269-1278. [20] Katz M J, Mondloch J E, Farha O K, et al.Simple and compelling biomimetic metal-organic framework catalyst for the degradation of nerve agent simulants[J]. Angewandte Chemie International Edition, 2013, 126(2): 507-511. [21] 戴栋, 宁文军, 邵涛, 等. 大气压低温等离子体的研究现状与发展趋势[J]. 电工技术学报, 2017, 32(20): 1-9. Dai Dong, Ning Wenjun, Shao Tao, et al.Research status and development trend of atmospheric pressure low temperature plasma[J]. Transactions of China Electrotechnical Society, 2017, 32(20): 1-9. [22] 王志强, 曹云霄, 邢政伟, 等. 高压脉冲放电破碎菱镁矿石的实验研究[J]. 电工技术学报, 2019, 34(4): 863-870. Wang Zhiqiang, Cao Yunxiao, Xin Zhengwei, et al.Experimental study on crushing magnesite ore by high voltage pulse discharge[J]. Transactions of China Electrotechnical Society, 2019, 34(4): 863-870. [23] 吴世林, 杨庆, 邵涛. 低温等离子体表面改性电极材料对液体电介质电荷注入的影响[J]. 电工技术学报, 2019, 34(16): 3494-3503. Wu Shilin, Yang Qin, Shao Tao.Effect of low temperature plasma surface modified electrode materials on charge injection into liquid dielectrics[J]. Transactions of China Electrotechnical Society, 2019, 34(16): 3494-3503. [24] Bian Xingming, Zhu Junyu, Yang Wei, et al.The role of low air pressure in the variation of negative corona-generated space charge in a rod to plane electrode[J]. High Voltage, 2018, 3(2): 126-132. [25] 徐玉韬, 谈竹奎, 肖永, 等. 自阻型子模块MMC的实时仿真分析[J]. 电力系统及其自动化学报, 2019, 31(7): 105-109. Xu Yutao, Tan Zhukui, Xiao Yong, et al.Real time simulation analysis of self resistance sub module MMC[J]. Journal of Electrical Engineering and Its Automation Compulsory, 2019, 31(7): 105-109. [26] 邵涛, 章程, 王瑞雪, 等. 大气压脉冲气体放电与等离子体应用[J]. 高电压技术, 2016, 42(3): 685-705. Shao Tao, Zhang Cheng, Wang Ruixue, et al.Atmospheric pressure pulsed gas discharge and plasma applications[J]. High Voltage Engineering, 2016, 42(3): 685-705. [27] 梁晨光, 王宾, 李凤婷, 等. 高压线路单相弧光接地对数仿真模型数据修正算法[J]. 电力系统自动化, 2019, 43(4): 126-131. Liang Chenguang, Wang Bin, Li Fengting, et al.Data correction algorithm for logarithmic simulation model of single phase arc grounding of high voltage transmission lines[J]. Automation of Electric Power Systems, 2019, 43(4): 126-131. [28] 史曜炜, 周若瑜, 崔行磊, 等. 不同电源激励下共面介质阻挡放电特性实验[J]. 电工技术学报, 2018, 33(22): 5371-5380. Shi Yaowei, Zhou Ruoyu, Cui Xinglei, et al.Experiments on coplanar dielectric barrier discharge characteristics under different power supply excitations[J]. Transactions of China Electrotechnical Society, 2018, 33(22): 5371-5380. [29] Park J, Henins I, Herrmann H W, et al.Gas breakdown in an atmospheric pressure radio-frequency capacitive plasma source[J]. Journal of Applied Physics, 2001, 89(1): 15-19. [30] 张波, 汪立峰, 刘峰, 等. 交流和纳秒脉冲激励氦气中等离子体射流阵列放电特性比较[J]. 电工技术学报, 2019, 34(6): 1319-1328. Zhang Bo, Wang Lifeng, Liu Feng, et al.Comparison of discharge characteristics of plasma jet arrays excited by AC and nanosecond pulses in helium[J]. Transactions of China Electrotechnical Society, 2019, 34(6): 1319-1328. [31] Laroussi M, Akan T.Arc-free atmospheric pressure cold plasma jets: a review[J]. Plasma Processes and Polymers, 2007, 4(9): 777-788. [32] Ji Shiqi, Zhang Zheyu, Wang Fred.Overview of high voltage SiC power semiconductor devices: develop-ment and application[J]. CES Transactions on Electrical Machines and Systems, 2017, 1(3): 254-264. [33] Ding Li, Lian Yujuan, Li Yunwei.Multilevel current source converters for high power medium voltage applications[J]. CES Transactions on Electrical Machines & Systems, 2017, 1(3): 306-314. [34] 王晓玲, 高远, 张帅, 等. 脉冲参数对介质阻挡放电等离子体CH4干重整特性影响的实验[J]. 电工技术学报, 2019, 34(6): 215-223. Wang Xiaolin, Gao Yuan, Zhang Shuai, et al.Effects of pulse parameters on dry reforming characteristics of dielectric barrier discharge plasma CH4[J]. Transactions of China Electrotechnical Society, 2019, 34(6): 215-223. [35] Pascal S, Moussa D, Hnatiuc E, et al.Plasma chemical degradation of phosphorous-containing warfare agents simulants[J]. Journal of Hazardous Materials, 2010, 175(1-3): 1037-1041. [36] Zhu Wenzhao, Wang Bairong, Xi Hailing, et al.Decontamination of VX surrogate malathion by atmospheric pressure radio-frequency plasma jet[J]. Plasma Chemistry and Plasma Processing, 2010, 30(3): 381-389. [37] Herrmann H W, Henins I, Park J, et al.Decontamination of chemical and biological warfare (CBW) agents using an atmospheric pressure plasma jet (APPJ)[J]. Physics of Plasmas, 1999, 6(5): 2284-2289. [38] Herrmann H W, Selwyn G S, Henins I, et al.Chemical warfare agent decontamination studies in the plasma decon chamber[J]. IEEE Transactions on Plasma Science, 2002, 30(4): 1460-1470. [39] Herrmann H W. Atmospheric-pressure plasma decontamination/sterilization chamber: Official Gazette of the United States Patent & Trademark Office Patents, US, 6228330 B1, 2001, 8(5)[P]. [40] Kim Y H, Choi Y H, Kim J H, et al.Decontamination of radioactive metal surface by atmospheric pressure ejected plasma source[J]. Surface & Coating Technology, 2003, 171(1-3): 317-320. [41] Moeller T M, Alexander M L, Engelhard M H, et al.Surface decontamination of simulated chemical warfare agents using a nonequilibrium plasma with off-gas monitoring[J]. IEEE Transactions on Plasma Science, 2002, 30(4): 1454-1459. [42] 李颖, 李战国, 刘志农, 等. 常压空气射流等离子体在表面洗消中的应用研究[J]. 公共安全中的化学问题研究进展, 2011, 2(1): 807-813. Li Yin, Li Zhanguo, Liu Zhinong, et al.Application of atmospheric air jet plasma in surface deconta-mination[J]. Research Progress of Chemical Problems in Public Safety, 2011, 2(1): 807-813. [43] 庄洪春, 孙鹞鸿, 彭燕昌, 等. 介质阻挡放电产生等离子体技术研究[J]. 高电压技术, 2002, 28(增刊): 57-58. Zhuang Hongchun, Sun Yaohong, Peng Yanchang, et al.Study on plasma generation by dielectric barrier discharge[J]. High Voltage Engineering, 2002, 28(S1): 57-58. [44] 高远, 张帅, 王瑞雪, 等. 脉冲介质阻挡放电等离子体催化CH4直接转化[J]. 电工技术学报, 2017, 32(2): 61-69. Gao Yuan, Zhang Shuai, Wang Ruixue, et al.Direct conversion of CH4 catalyzed by pulsed dielectric barrier discharge plasma[J]. Transactions of China Electrotechnical Society, 2017, 32(2): 61-69. [45] 李锻, 刘明辉, 吴彦, 等. 双极性脉冲高压介质阻挡放电降解氯苯和甲苯[J]. 中国环境科学, 2006, 26(7): 23-26. Li Duan, Liu Minghui, Wu Yan, et al.Degradation of chlorobenzene and toluene by bipolar pulsed high voltage dielectric barrier discharge[J]. Environmental Science in China, 2006, 26(7): 23-26. [46] 郝艳捧, 王晓蕾, 阳林, 等. 大气压氦气介质阻挡多脉冲辉光放电的形成条件[J]. 电工技术学报, 2009, 24(9): 28-32. Hao Yanpeng, Wang Xiaolei, Yang Lin, et al.Formation conditions of dielectric barrier multi pulse glow discharge in He at atmospheric pressure[J]. Transactions of China Electrotechnical Society, 2009, 24(9): 28-32. [47] 李壮, 底兰波, 于锋, 等. 冷等离子体强化制备金属催化剂研究进展[J]. 物理学报, 2018, 67(21): 40-51. Li Zhuang, Di Lanbo, Yu Feng, et al.Progress in preparation of metal catalysts by cold plasma intensification[J]. Journal of Physics, 2018, 67(21): 40-51. [48] Qi Fei, Li Yiyang, Zhou Rusen, et al.Uniform atmospheric pressure plasmas in a 7 mm air gap[J]. Applied Physics Letters, 2019, 115: 194101. [49] 唐诗雅, 刘全桢, 王世强, 等. 大气压脉冲介质阻挡放电等离子体研究进展[J]. 安全、健康和环境, 2019, 19(7): 70-74. Tang Shiya, Liu Quanzhen, Wang Shiqiang, et al.Progress in atmospheric pressure pulsed dielectric barrier discharge plasma[J]. Safety, Health and Environment, 2019, 19(7): 70-74. [50] 顾信鹏, 方志, 钱晨, 等. 气液两相介质阻挡放电影响因素研究[J]. 真空科学与技术学报, 2014, 34(8): 828-835. Gu Xinpeng, Fang Zhi, Qaian Chen, et al.Study on the influence factors of barrier discharge in gas-liquid two-phase media[J]. Journal of Vacuum Science and Technology, 2014, 34(8): 828-835. [51] 孙岩洲, 邱毓昌, 丁卫东. 电源频率对介质阻挡放电的影响[J]. 高电压技术, 2002, 28(11): 43, 53. Sun Yanyou, Qiu Yuchang, Ding Weidong. Effect of power supply frequency on dielectric barrier discharge[J]. High Voltage Engineering, 2002, 28(11): 43, 53. [52] 王春义, 牟宏, 柳璐, 等. 可再生能源和特高压接入下的区域电网可靠性和稳定性评估[J]. 电力系统及其自动化学报, 2019, 31(1): 99-104. Wang Chunyi, Mou Hong, Liu Lu, et al.Reliability and stability assessment of regional power grid with renewable energy and UHV access[J]. Journal of Electrical Engineering and Its Automation Compulsory, 2019, 31(1): 99-104. [53] Zhang Chunpeng, Zhao Zhengming.Dual-timescale control for power electronic zigzag transformer[J]. CES Transactions on Electrical Machines & Systems, 2017, 1(3): 315-321. [54] 吴春笃, 周建军, 储金宇, 等. 强电离放电等离子体洗消沙林模拟剂 DMMP 试验[J]. 江苏大学学报: 自然科学版, 2009, 30(6): 623-626. Wu Chundu, Zhou Jianjun, Chu Jinyu, et al.Experimental study on decontamination of sarin simulators by strong ionization discharge plasma[J]. Journal of Jiangsu University: Natural Science Edition, 2009, 30(6): 623-626. [55] 吴春笃, 周建军, 储金宇, 等. 强电离放电气体洗消 DMMP 机理研究[J]. 化学学报, 2010, 68(12): 1235-1240. Wu Chundu, Zhou Jianjun, Chu Jinyu, et al.Study on the mechanism of strong ionization discharge gas washing DMMP[J]. Journal of Chemistry, 2010, 68(12): 1235-1240. [56] Kim D B, Gweon B, Moon S Y, et al.Decontamination of the chemical warfare agent simulant dimethyl methylphosphonate by means of large-area low-temperature atmospheric pressure plasma[J]. Current Applied Physics, 2009, 9(5): 1093-1096. [57] Jarrige J, Vervisch P.Destruction of simulated chemical warfare agents in non-thermal atmospheric-pressure air plasma[J]. Prague, Czech Republic, 2007, 56(16): 1414-1416. [58] 李战国, 胡真, 王守国, 等. 介质阻挡放电等离子体洗消芥子气染毒空气的研究[J]. 环境科学学报, 2007, 27(3): 522-528. Li Zhanguo, Hu Zhen, Wang Shouguo, et al.Study on decontamination of mustard gas contaminated air by dielectric barrier discharge plasma[J]. Journal of Environmental Science, 2007, 27(3): 522-528. [59] Li Zhanguo.Decomposition of toxic gas by pulse corona plasma[J]. Environmental Chemistry, 2012, 31(6): 869-873. [60] 李战国, 朱勇兵, 朱晓明, 等. 流光电晕放电对 2-氯乙基乙基硫醚气体的降解研究[C]//中国环境科学学会学术年会论文, 昆明, 2013: 4514-4517. [61] Sahni M, Locke B R.Degradation of chemical warfare agent simulants using gas-liquid pulsed streamer discharges[J]. Journal of Hazardous Materials, 2006, 137(2): 1025-1034. [62] 杨丽敏, 刘海玉, 谢创举, 等. 微波放电对活性炭脱硝的影响[J]. 中国电机工程学报, 2018, 38(21): 6375-6382. Yang Limin, Liu Haiyu, Xie Chuangju, et al.Effect of microwave discharge on denitration of activated carbon[J]. Proceedings of the CSEE, 2018, 38(21): 6375-6382. [63] Uhm H S, Cho S C, Hong Y C, et al.Destruction of dimethyl methylphonate using a microware plasma torch[J]. Applied Physics Letters, 2008, 92(7): 7153. [64] 陈鹏, 陶雷, 谢怡冰, 等. 低温等离子体协同催化降解挥发性有机物的研究进展[J]. 化工进展, 2019, 38(9): 4284-4294. Chen Peng, Tao Lei, Xie Yibing, et al.Research progress of low temperature plasma assisted catalytic degradation of volatile organic compounds[J]. Progress in Chemical Industry, 2019, 38(9): 4284-4294. [65] 陈永铎, 王晓晨, 李颖, 等. 等离子体辅助 Fenton 洗消甲基膦酸二甲酯水溶液[J]. 浙江大学学报: 工学版, 2013 (12): 2195-2201. Chen Yongduo, Wang Xiaochen, Li Yin, et al.Plasma assisted Fenton decontamination of dimethyl methylphosphonate aqueous solution[J]. Journal of Zhejiang University: Engineering Edition, 2013 (12): 2195-2201. [66] 周远翔, 刘心曲, 王明渊, 等. 空气沿面介质阻挡放电中活性粒子成分及其影响因素[J]. 高电压技术, 2016, 42(2): 421-427. Zhou Yuanxiang, Liu Xinqu, Wang Mingyuan, et al.Composition and influencing factors of active particles in air surface dielectric barrier discharge[J]. High Voltage Engineering, 2016, 42(2): 421-427. [67] 邵涛, 严萍. 大气压气体放电及其等离子体应用[M]. 北京: 科学出版社, 2015. [68] 吴淑群, 董熙, 卢新培, 等. 基于激光诱导荧光法诊断大气压低温等离子体射流中OH自由基和O原子的时空分布[J]. 电工技术学报, 2017, 32(8): 82-94. Wu Shuqun, Dong Xi, Lu Xinpei, et al.Diagnosis of temporal and spatial distribution of OH radical and O atom in atmospheric pressure low temperature plasma jet based on laser induced fluorescence[J]. Transactions of China Electrotechnical Society, 2017, 32(8): 82-94. [69] 荣俊锋, 李泰广, 史同上, 等. 低温等离子体净化苯甲酸废水研究[J]. 应用化工, 2019, 48(7): 1592-1594. Rong Junfeng, Lao Taiguang, Shi Tongshang, et al.Study on purification of benzoic acid wastewater by low temperature plasma[J]. Applied Chemical Industry, 2019, 48(7): 1592-1594.
2021, Vol. 36 
