等离子体合成氨技术研究进展

doi:10.16085/j.issn.1000-6613.2017-1303

摘要/Abstract

摘要： 合成氨工业极大地影响着人类的发展进程，但是传统的合成氨过程需要在高温高压条件下进行。因此，如何降低反应温度和压力一直是该领域的研究热点。等离子体合成氨技术相比传统合成氨技术具有反应条件温和、原料廉价易得、不排放温室气体等优点，这种技术被认为具有很大的发展潜力。本文综述了等离子合成氨技术的发展及近期取得的成果，包括不同放电方式、不同反应器、不同放电参数和进气比例等参数条件对合成氨效果的影响，并对催化剂在等离子体合成氨技术中的作用进行了总结和讨论。根据目前等离子体合成氨技术取得的成果，指出其发展方向有以下几点：使用H₂O和CH₄作为氢源；开发钌基催化剂等贵金属催化剂；设计和制造适合于等离子体合成氨技术的反应器；匹配大功率的电源设备。

关键词: 等离子体技术, 介质阻挡放电, 合成氨, 催化剂, 优化, 反应器

Abstract: The ammonia industry has a great influence on the process of human development. However,the traditional ammonia synthesis needs to be carried out under high temperature and pressure. Therefore,reducing the reaction temperature and pressure has been a hot research topic in this field. Compared with the traditional method,ammonia synthesis using plasma has the advantages of mild reaction conditions,cheap raw materials and non-emission of greenhouse gases,therefore this technology is considered to have great potential. In this paper,the present situation of ammonia synthesis by plasma was reviewed,including using different discharge methods,different reactors,different discharge parameter and feed gas ratio conditions. Meanwhile,the effect of catalysts on the ammonia synthesis with plasma was summarized and discussed. According to current achievements of ammonia synthesis with plasma technology,it is considered that the development directions are as follows:the use of H₂O and CH₄ as hydrogen sources;the development of precious metal catalysts such as ruthenium-based catalysts;the design and manufacture of reactors suitable for synthesis ammonia with plasma and the matching of high-power power equipment.

Key words: plasma technology, dielectric barrier discharge, ammonia synthesis, catalyst, optimization, reactors

中图分类号:

TQ113.26

冯嘉予, 宁平, 孙鑫, 王驰, 李坤林, 李凯. 等离子体合成氨技术研究进展[J]. 化工进展, 2018, 37(05): 1968-1977.

FENG Jiayu, NING Ping, SUN Xin, WANG Chi, LI Kunlin, LI Kai. Research review of non-thermal plasma technology for ammonia synthesis[J]. Chemical Industry and Engineering Progress, 2018, 37(05): 1968-1977.

参考文献

[1] KITANO M,INOUE Y,YAMAZAKI Y,et al. Ammonia synthesis using a stable electride as an electron donor and reversible hydrogen store[J]. Nature Chemistry,2012,4(11):934-940.
[2] AFIF A,RADENAHMAD N,CHEOK Q,et al. Ammonia-fed fuel cells:a comprehensive review[J]. Renewable & Sustainable Energy Reviews,2016,60:822-835.
[3] MARNELLOS G,STOUKIDES M. Ammonia synthesis at atmospheric pressure[J]. Science,1998,282(5386):98-100.
[4] SHAFAIEE S,TOPAL E. When will fossil fuel reserves be diminished?[J]. Energy Policy,2009,37(1):181-189.
[5] 蒋德军. 合成氨工艺技术的现状及其发展趋势[J]. 现代化工,2005,25(8):9-14. JIANG D J. Present situation and development of technology for ammonia synthetic process[J]. Modern Chemical Industry,2005,25(8):9-14.
[6] 颜鑫. 我国合成氨工业的回顾与展望——纪念世界合成氨工业化100周年[J]. 化肥设计,2013(5):1-6. YAN X. Retrospect and prospect of synthetic ammonia industry in China——commemorating the 100th anniversary of synthetic ammonia industry in the world[J]. Chemical Fertilizer Design,2013(5):1-6.
[7] ZHANG C,CHEN J,WEN Z. Assessment of policy alternatives and key technologies for energy conservation and water pollution reduction in China's synthetic ammonia industry[J]. Journal of Cleaner Production,2011,25:96-105.
[8] 刘化章. 合成氨工业:过去、现在和未来——合成氨工业创立100周年回顾、启迪和挑战[J]. 化工进展,2013,32(9):1995-2005. LIU H Z. Ammonia synthesis industry:past,present and future——retrospect,enlightenment and challenge from 100 years of ammonia synthesis industry[J]. Chemical Industry and Engineering Progress,2013,32(9):1995-2005.
[9] 刘化章. 合成氨工业节能减排的分析[J]. 化工进展,2011,30(6):1147-1157. LIU H Z. Analysis of energy saving in ammonia synthesis industry[J]. Chemical Industry and Engineering Progress,2011,30(6):1147-1157.
[10] JAFARI R,ASADOLLAHI S,FARZANEH M. Applications of plasma technology in development of superhydrophobic surfaces[J]. Plasma Chemistry and Plasma Processing,2013,33(1):177-200.
[11] TENDERO C,TIXIER C,TRISTANT P,et al. Atmospheric pressure plasmas:a review[J]. Spectrochimica Acta Part B:Atomic Spectroscopy,2006,61(1):2-30.
[12] HONKALA K,HELLMAN A,REMEDIAKIS I N,et al. Ammonia synthesis from first-principles calculations[J]. Science,2005,307(5709):555.
[13] 李和平,于达仁,孙文廷,等. 大气压放电等离子体研究进展综述[J]. 高电压技术,2016,42(12):3697-3727. LI H P,YU D R,SUN W Y,et al. State-of-the-art of atmospheric discharge plasmas[J]. High Voltage Engineering,2016,42(12):3697-3727.
[14] GUO C,TANG F,CHEN J,et al. Development of dielectric-barrier-discharge ionization[J]. Analytical and Bioanalytical Chemistry,2015,407(9):2345-2364.
[15] 王新新. 介质阻挡放电及其应用[J]. 高电压技术,2009,35(1):1-11. WANG X X. Dielectric barrier discharge and its applications[J]. High Voltage Engineering,2009,35(1):1-11.
[16] 王燕,白敏冬,张芝涛,等. 强电离放电合成氨实验研究[J]. 大连海事大学学报,2002,28(2):59-62. WANG Y,BAI M D,ZHANG Z T,et al. Study on ammonia synthesis by strong electric field discharge[J]. Journal of Dalian Maritime University,2002,28(2):59-62.
[17] 詹科萍,白敏冬,高洪辉,等. 强电场放电CH₄与N₂合成方法的研究[J]. 高电压技术,2006,32(5):60-62. ZAHAN K P,BAI M D,GAO H H,et al. Synthesis of CH₄ and N₂ by the DBD discharge[J]. High Voltage Engineering,2006,32(5):60-62.
[18] BAI M D,ZHANG Z T,BAI M,et al. Synthesis of ammonia using CH₄/N₂,plasmas based on micro-gap discharge under environmentally friendly condition[J]. Plasma Chemistry and Plasma Processing,2008,28(4):405-414.
[19] GOMEZR AMIREZ A,COTRINO J,LAMBERT R M,et al. Efficient synthesis of ammonia from N₂ and H₂ alone in a ferroelectric packed-bed DBD reactor[J]. Plasma Sources Science & Technology,2015,24(6):065011.
[20] XIE D Y,SUN Y,ZHU T L,et al. Ammonia synthesis and by-product formation from H₂O,H₂ and N₂ by dielectric barrier discharge combined with an Ru/Al₂O₃ catalyst[J]. RSC Advances,2016,6(107):105338-105346.
[21] 李成榕,王新新. 大气压下的辉光放电[J]. 高电压技术,2002,28(b12):41-43. LI C R,WANG X X. Atmospheric pressure glow discharge[J]. High Voltage Engineering,2002,28(b12):41-43.
[22] WANG X,ZHOU M,JIN X. Application of glow discharge plasma for wastewater treatment[J]. Electrochimica Acta,2012,83(12):501-512.
[23] YIN K S,VENUGOPALAN M. Plasma chemical synthesis. I. Effect of electrode material on the synthesis of ammonia[J]. Plasma Chemistry and Plasma Processing,1983,3(3):343-350.
[24] 白敏冬,张芝涛,白希尧,等. 强电场放电常压合成NH₃研究[J]. 大连海事大学学报,1999,25(1):84-87,110. BAI M D,ZHANG Z T,BAI X X,et al. Study on synthesis NH₃ at normal pressure by the strong electric field discharge[J]. Journal of Dalian Maritime University,1999,25(1):84-87,110.
[25] CALZADA M D,MOISAN M,GAMERO A,et al. Experimental investigation and characterization of the departure from local thermodynamic equilibrium along a surface-wave-sustained discharge at atmospheric pressure[J]. Journal of Applied Physics,1996,80(1):46-55.
[26] NAKAJIMA J,SEKIGUCHI H. Synthesis of ammonia using microwave discharge at atmospheric pressure[J]. Thin Solid Films,2008,516(13):4446-4451.
[27] TURNER M M. Collisionless heating in radio-frequency discharges:a review[J]. Journal of Physics D:Applied Physics,2009,42(19):194008.
[28] 赵亚楠. 射频等离子体氨合成及其动力学研究[D]. 重庆:重庆大学,2013. ZHAO Y N. Ammonia synthesis under radio frequency plasma and the kinetics research[D]. Chongqing:Chongqing University,2013.
[29] HARUYAMA T,NAMISE T,SHIMOSHIMIZU N,et al. Non-catalyzed one-step synthesis of ammonia from atmospheric air and water[J]. Green Chemistry,2016,18(16):4536-4541.
[30] AIHARA K,AKIYAMA M,DEGUCHI T,et al. Remarkable catalysis of a wool-like copper electrode for NH₃ synthesis from N₂ and H₂ in non-thermal atmospheric plasma[J]. Chemical Communications,2016,52(93):13560-13563.
[31] MIZUSHIMA T,MATSUMOTO K,OHKITA H,et al. Catalytic effects of metal-loaded membrane-like alumina tubes on ammonia synthesis in atmospheric pressure plasma by dielectric barrier discharge[J]. Plasma Chemistry and Plasma Processing,2007,27(1):1-11.
[32] HONG J,ARAMESH M,SHIMONI O,et al. Plasma catalytic synthesis of ammonia using functionalized-carbon coatings in an atmospheric-pressure non-equilibrium discharge[J]. Plasma Chemistry and Plasma Processing,2016,36(4):917-940.
[33] PENG P,LI Y,CHENG Y,et al. Atmospheric pressure ammonia synthesis using non-thermal plasma assisted catalysis[J]. Plasma Chemistry and Plasma Processing,2016,36(5):1201-1210.
[34] BAI M,BAI X,ZHANG Z,et al. Synthesis of ammonia in a strong electric field discharge at ambient pressure[J]. Plasma Chemistry and Plasma Processing,2000,20(4):511-520.
[35] BAI M D,ZHANG Z,BAI X,et al. Plasma synthesis of ammonia with a microgap dielectric barrier discharge at ambient pressure[J]. IEEE Transactions on Plasma Science,2004,31(6):1285-1291.
[36] KIM H,TERAMOTO Y,OGATA A,et al. Atmospheric-pressure nonthermal plasma synthesis of ammonia over ruthenium catalysts[J]. Plasma Processes & Polymers,2016,36(5):1201-1210.
[37] ⅡTSUKA Y,YAMAUCHI H,SATO S,et al. Ammonia production from solid urea using non-thermal plasma[J]. IEEE Transactions on Industry Applications,2012,48:872-877.
[38] SAADATIOU N,JJAFARI A,SAHEBDELFAR S. Ruthenium nanocatalysts for ammonia synthesis:a review[J]. Chemical Engineering Communications,2015,202(4):420-448.
[39] MOHA V,LEITNER W,HOLSCHER M. NH₃ synthesis in the N₂/H₂ reaction system using cooperative molecular tungsten/rhodium catalysis in ionic hydrogenation:a DFT study[J]. Chemistry,2016,22(8):2624.
[40] SEETHARAMULU P,KUMAR V S,PADMASRI A H,et al. A highly active nano-Ru catalyst supported on novel Mg-Al hydrotalcite precursor for the synthesis of ammonia[J]. Catalysis Today,2007,141(1/2):94-98.
[41] 刘化章,李小年. 合成氨催化技术与工艺进展[J]. 现代化工,2004,24(2):7-11. LIU H Z,LI X N. Advance in catalytic technology and process for ammonia synthesis[J]. Modern Chemical Industry,2004,24(2):7-11.
[42] 诸葛绍渊. 常压介质阻挡放电等离子体协同催化合成氨应用基础研究[D]. 杭州:浙江工业大学,2015. ZHUGE S Y. Ammonia synthesis using atmosphere DBD plasma coupled with catalysis[D]. Hangzhou:Zhejiang University of Technology,2015.
[43] AKAY G,ZHANG K. Process intensification in ammonia synthesis using novel co-assembled supported micro-porous catalysts promoted by non-thermal plasma[J]. Industrial & Engineering Chemistry Research,2016,56(2):457-468.
[44] PFENDER E. Thermal plasma technology:where do we stand and where are we going?[J]. Plasma Chemistry & Plasma Processing,1999,19(1):1-31.
[45] 罗跃辉,杨兰均,冯允平,等. 放电等离子体空气灭菌净化技术的研究[J]. 高电压技术,2001,27(5):39-40. LUO Y H,YANG L J,FENG Y P,et al. Study on the technology of air sterilization by discharge plasmas[J]. High Voltage Engineering,2001,27(5):39-40.
[46] 沈红梅,任荣,顾璠. 大功率介质阻挡等离子体电源特性及工业应用研究[J]. 电源技术应用,2009(7):12-16. SHEN H M,REN R,GU F. Characteristics and industrial application of high power supply used in dielectric barrier discharge[J]. Power Supply Technologies and Applications,2009(7):12-16.
[47] 林杰. 基于DSP的低温等离子体电源控制系统设计[D]. 北京:北京交通大学,2009. LIN J. The design of control system of the plasma power supply for sewage treatment based on DSP[D]. Beijing:Beijing Jiaotong University,2009.
[48] 韩银娟,周海东,马立新,等. 低温等离子体电源的设计及有机物降解研究[J]. 信息技术,2015(2):38-41. HAN Y J,ZHOU H D,MA L X,et al. Design and application of a power supply of non-thermal plasma for the degradation of organic substance[J]. Information Technology,2015(2):38-41.
[49] 朱志杰,张贵新,刘亮,等. 用于产生等离子体的高压脉冲电源的研制[J]. 高电压技术,2007,33(2):28-31. ZHU Z J,ZHANG G X,LIU L,et al. Development of a pulse generator for exciting plasma[J]. High Voltage Engineering,2007,33(2):28-31.
[50] 刘海鹏,易波. 空气中低温等离子体生成电源的研究[J]. 中国科技信息,2010(18):48-49. LIU H P,YI B. Research on air NTP power supply[J]. China Science and Technology Information,2010(18):48-49.