Article(id=1236372359884633028, tenantId=1146029695717560320, journalId=1210938733613449225, issueId=1236372356109751006, articleNumber=null, orderNo=null, doi=10.19666/j.rlfd.202505093, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1749139200000, receivedDateStr=2025-06-06, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1772703741283, onlineDateStr=2026-03-05, pubDate=1756051200000, pubDateStr=2025-08-25, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1772703741283, onlineIssueDateStr=2026-03-05, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1772703741283, creator=13701087609, updateTime=1772703741283, updator=13701087609, issue=Issue{id=1236372356109751006, tenantId=1146029695717560320, journalId=1210938733613449225, year='2025', volume='54', issue='8', pageStart='1', pageEnd='174', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1772703740384, creator=13701087609, updateTime=1772788131769, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1236726319342481872, tenantId=1146029695717560320, journalId=1210938733613449225, issueId=1236372356109751006, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1236726319342481873, tenantId=1146029695717560320, journalId=1210938733613449225, issueId=1236372356109751006, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=131, endPage=141, ext={EN=ArticleExt(id=1236372360161457101, articleId=1236372359884633028, tenantId=1146029695717560320, journalId=1210938733613449225, language=EN, title=Enhancement of ammonia combustion characteristics by coupling methane with plasma, columnId=1236372358878000047, journalTitle=Thermal Power Generation, columnName=Carbon neutral fuel coupled combustion and emission control, runingTitle=null, highlight=null, articleAbstract=

To tackle the challenges associated with the poor combustion performance of ammonia fuels and the high NOx emissions in exhaust gases, experimental research on enhancing ammonia combustion through the use of a swirling burner combined with a gliding arc plasma generator was carried out. The effects of various combustion enhancement methods, including methane-assisted combustion, plasma-assisted combustion, and plasma-coupled methane-assisted combustion, on the combustion characteristics of NH3 swirling flames and the generation of NO were investigated. The experimental results indicated that, compared with the methane-assisted combustion, both plasma-coupled methane-assisted combustion and plasma-assisted combustion significantly enhanced the stability of ammonia combustion. This improvement was evidenced by a substantial expansion of the stable combustion limit range of the NH3 swirling flame, enabling normal combustion within an NH3/Air equivalence ratio range of 0~5.0. In comparison to single methane-assisted or plasma-assisted combustion, plasma-coupled methane-assisted combustion (with a plasma power of 0.8 kW and a methane flow rate of 1 L/min) significantly enhanced the active species Hα and OH generated by the discharge, thereby strengthening the chemical effects in plasma-assisted combustion. Under these conditions, the NO emission mass concentration in the exhaust gases rapidly decreased from over 7 000 mg/m3 to approximately 100 mg/m3 as the NH3/Air equivalence ratio was increased from 0.6 to 0.8. Furthermore, the gas temperature under these conditions was only slightly lower than that observed in pure plasma-assisted combustion, where the flame temperature of ammonia combustion could reach up to approximately 2 030 K.

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针对氨燃料燃烧性能差和尾气NOx排放量高的问题,在耦合滑动电弧等离子体发生器的旋流燃烧器上开展增强氨燃烧的实验,研究了甲烷助燃、等离子体助燃以及等离子体耦合甲烷助燃等不同助燃方式对氨燃烧旋流火焰特性和NO生成特性的影响。实验结果表明:相较于甲烷助燃,等离子体耦合甲烷助燃和等离子体助燃都能有效提高氨燃烧稳定性,扩展氨旋流火焰稳燃极限范围,在NH3/空气当量比为0~5.0的范围内均可正常燃烧;与单一的甲烷助燃及等离子体助燃相比,等离子体耦合甲烷助燃(等离子体功率为0.8 kW、甲烷输入量为1 L/min)工况下放电产生的Hα及OH活性粒子能够得到显著增强,进而增强了等离子体助燃中的化学效应,并且在NH3/空气当量比从0.6增加至0.8时,尾气中NO排放质量浓度从超过7 000 mg/m3开始快速下降至100 mg/m3左右。此外,气体温度只比单纯等离子体助燃工况稍低,单纯等离子体助燃工况下的氨燃烧火焰温度最高可达2 030 K左右。

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林启富(1987),男,博士,副研究员,主要研究方向为低温等离子体物理、等离子体助燃、氢氨能应用,
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钟世龙(2000),男,硕士研究生,主要研究方向为滑动电弧等离子体和甲烷强化氨燃烧技术,

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Ammonia combustion experimental conditions

, figureFileSmall=null, figureFileBig=null, tableContent=
助燃方式等离子体功率/kW甲烷流量/(L·min–1)
甲烷助燃(Case1)05
等离子体耦合甲烷助燃(Case2)0.24
等离子体耦合甲烷助燃(Case3)0.43
等离子体耦合甲烷助燃(Case4)0.62
等离子体耦合甲烷助燃(Case5)0.81
等离子体助燃(Case6)1.00
), ArticleFig(id=1236726412229529730, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1236372359884633028, language=CN, label=表1, caption=

氨燃烧实验工况

, figureFileSmall=null, figureFileBig=null, tableContent=
助燃方式等离子体功率/kW甲烷流量/(L·min–1)
甲烷助燃(Case1)05
等离子体耦合甲烷助燃(Case2)0.24
等离子体耦合甲烷助燃(Case3)0.43
等离子体耦合甲烷助燃(Case4)0.62
等离子体耦合甲烷助燃(Case5)0.81
等离子体助燃(Case6)1.00
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等离子体耦合甲烷增强氨燃烧特性研究
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钟世龙 1, 2 , 林启富 2 , 吴殿武 2 , 宋亚伟 2 , 刘成周 2 , 武晨 2, 3 , 陈龙威 2 , 李振阳 2 , 陈维晔 2 , 冯汉升 2, 4 , 罗广南 2, 4
热力发电 | 碳中性燃料耦合燃烧与排放控制 2025,54(8): 131-141
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热力发电 | 碳中性燃料耦合燃烧与排放控制 2025, 54(8): 131-141
等离子体耦合甲烷增强氨燃烧特性研究
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钟世龙1, 2 , 林启富2 , 吴殿武2, 宋亚伟2, 刘成周2, 武晨2, 3, 陈龙威2, 李振阳2, 陈维晔2, 冯汉升2, 4, 罗广南2, 4
作者信息
  • 1.安徽工业大学能源与环境学院,安徽 马鞍山 243002
  • 2.合肥综合性国家科学中心能源研究院(安徽省能源实验室),安徽 合肥 230031
  • 3.安徽理工大学地球与环境学院,安徽 淮南 232001
  • 4.中国科学院合肥物质科学研究院等离子体物理研究所,安徽 合肥 230031
  • 钟世龙(2000),男,硕士研究生,主要研究方向为滑动电弧等离子体和甲烷强化氨燃烧技术,

通讯作者:

林启富(1987),男,博士,副研究员,主要研究方向为低温等离子体物理、等离子体助燃、氢氨能应用,
Enhancement of ammonia combustion characteristics by coupling methane with plasma
Shilong ZHONG1, 2 , Qifu LIN2 , Dianwu WU2, Yawei SONG2, Chengzhou LIU2, Chen WU2, 3, Longwei CHEN2, Zhenyang LI2, Weiye CHEN2, Hansheng FENG2, 4, Guangnan LUO2, 4
Affiliations
  • 1.School of Energy and Environment, Anhui University of Technology, Maanshan 243002, China
  • 2.Institute of Energy, Hefei Comprehensive National Science Center (Anhui Provincial Energy Laboratory), Hefei 230031, China
  • 3.School of Earth and Environment, Anhui University of Science and Technology, Huainan 232001, China
  • 4.Institute of Plasma Physics, Hefei Institutes of Physical Science, Chinese Academy of Sciences, Hefei 230031, China
出版时间: 2025-08-25 doi: 10.19666/j.rlfd.202505093
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针对氨燃料燃烧性能差和尾气NOx排放量高的问题,在耦合滑动电弧等离子体发生器的旋流燃烧器上开展增强氨燃烧的实验,研究了甲烷助燃、等离子体助燃以及等离子体耦合甲烷助燃等不同助燃方式对氨燃烧旋流火焰特性和NO生成特性的影响。实验结果表明:相较于甲烷助燃,等离子体耦合甲烷助燃和等离子体助燃都能有效提高氨燃烧稳定性,扩展氨旋流火焰稳燃极限范围,在NH3/空气当量比为0~5.0的范围内均可正常燃烧;与单一的甲烷助燃及等离子体助燃相比,等离子体耦合甲烷助燃(等离子体功率为0.8 kW、甲烷输入量为1 L/min)工况下放电产生的Hα及OH活性粒子能够得到显著增强,进而增强了等离子体助燃中的化学效应,并且在NH3/空气当量比从0.6增加至0.8时,尾气中NO排放质量浓度从超过7 000 mg/m3开始快速下降至100 mg/m3左右。此外,气体温度只比单纯等离子体助燃工况稍低,单纯等离子体助燃工况下的氨燃烧火焰温度最高可达2 030 K左右。

氨稳燃  /  等离子体助燃  /  燃烧稳定性  /  光谱特性  /  尾气排放

To tackle the challenges associated with the poor combustion performance of ammonia fuels and the high NOx emissions in exhaust gases, experimental research on enhancing ammonia combustion through the use of a swirling burner combined with a gliding arc plasma generator was carried out. The effects of various combustion enhancement methods, including methane-assisted combustion, plasma-assisted combustion, and plasma-coupled methane-assisted combustion, on the combustion characteristics of NH3 swirling flames and the generation of NO were investigated. The experimental results indicated that, compared with the methane-assisted combustion, both plasma-coupled methane-assisted combustion and plasma-assisted combustion significantly enhanced the stability of ammonia combustion. This improvement was evidenced by a substantial expansion of the stable combustion limit range of the NH3 swirling flame, enabling normal combustion within an NH3/Air equivalence ratio range of 0~5.0. In comparison to single methane-assisted or plasma-assisted combustion, plasma-coupled methane-assisted combustion (with a plasma power of 0.8 kW and a methane flow rate of 1 L/min) significantly enhanced the active species Hα and OH generated by the discharge, thereby strengthening the chemical effects in plasma-assisted combustion. Under these conditions, the NO emission mass concentration in the exhaust gases rapidly decreased from over 7 000 mg/m3 to approximately 100 mg/m3 as the NH3/Air equivalence ratio was increased from 0.6 to 0.8. Furthermore, the gas temperature under these conditions was only slightly lower than that observed in pure plasma-assisted combustion, where the flame temperature of ammonia combustion could reach up to approximately 2 030 K.

ammonia stable combustion  /  plasma-assisted combustion  /  combustion stability  /  spectral characteristics  /  exhaust emission
钟世龙, 林启富, 吴殿武, 宋亚伟, 刘成周, 武晨, 陈龙威, 李振阳, 陈维晔, 冯汉升, 罗广南. 等离子体耦合甲烷增强氨燃烧特性研究. 热力发电, 2025 , 54 (8) : 131 -141 . DOI: 10.19666/j.rlfd.202505093
Shilong ZHONG, Qifu LIN, Dianwu WU, Yawei SONG, Chengzhou LIU, Chen WU, Longwei CHEN, Zhenyang LI, Weiye CHEN, Hansheng FENG, Guangnan LUO. Enhancement of ammonia combustion characteristics by coupling methane with plasma[J]. Thermal Power Generation, 2025 , 54 (8) : 131 -141 . DOI: 10.19666/j.rlfd.202505093
在“双碳”战略目标的背景下,亟需以低碳清洁能源替代传统化石燃料。氢作为一种零碳排放、高热值的燃料,正日益受到广泛关注。然而,氢的运输和储存还面临诸多难题,一直未能大规模应用。氨作为一种储氢载体,具备体积能量密度高、辛烷值高和易液化储运等优势[1],且在完全燃烧的情况下,不会产生碳排放,氨能为“双碳”目标的实现提供了新路径。然而,氨气的燃烧速度慢,且高氮量会增加NOx排放风险。因此,提高氨燃烧的稳定性和降低NOx排放成为氨燃烧利用的关键[2]
针对氨燃料燃烧性能差等问题,已经发展了系列氨气燃烧强化措施,主要有掺烧高活性燃料[3-6]、富氧燃烧[7]和等离子体辅助燃烧[8-10]等。氨气与甲烷、氢气等高化学反应活性燃料掺烧,不仅可以缩短着火延迟时间、扩展可燃极限范围,还能显著提高火焰传播速度,但存在增加NOx生成量的风险。Giovanni等人[11]采用旋流燃烧器进行纯氨和氨/甲烷混合燃料的MILD燃烧实验研究,发现氨/甲烷混合燃料的燃烧极限范围更广,但NOx排放量更高。Filipe等人[12]在预混层流燃烧器进行NH3/CH4/空气混合燃烧实验,获得了NOx排放量与燃料混合物中NH3摩尔分数的关联关系,发现在固定NH3/空气当量比φ下,NOx排放量随着NH3摩尔分数的增加呈现先上升后下降趋势,且只要添加NH3,在NH3/空气当量比范围内(φ=0.8~1.0),所测的NOx排放量都很高(2 000~4 000 mg/m3),在所测NH3/CH4/空气当量比范围内(φ=0.8~1.0)NOx排放都很高(2 000~ 4 000 mg/m3),表明NH3/CH4/空气混燃虽能提高氨燃烧稳定性,但对NOx生成的控制仍未很好地解决。Yuze等人[13]对具有简化化学动力学机制的预混NH3/H2旋流火焰进行了三维数值模拟,发现在同一当量比下,添加H2能显著地提高混合燃料的层流燃烧速度,且与纯NH3相比,NH3/H2混合燃烧的NO排放量更高,并随着氢燃料的增加而升高。此外,Liu等人[14]在单旋流燃气涡轮机模型燃烧室中进行了富氧环境中的氨燃烧,发现富氧可以增强燃烧强度和火焰稳定性,使火焰根部稳定在燃烧器出口处。但纯氧生产成本较高,限制了其实际的工业燃烧应用。由于活性自由基可以通过加速关键路径的反应速率来增强燃烧,因此也有学者采用等离子体助燃的方式来提高氨燃烧的稳定性。Sun等人[15]研究了滑动电弧等离子体放电对NH3/CH4/空气混合燃料燃烧特性的实验研究,发现施加滑动电弧放电不仅能提供高频重复点火,还可以产生更多的OH自由基,提高了火焰稳定性,使得NH3/CH4预混燃烧的贫燃极限显著提高56%。Tang等人[16]研究了有无滑动电弧等离子体助燃方式对贫燃条件NH3/空气燃烧特性的影响,发现使用等离子体助燃方式能显著扩展贫燃吹熄极限。当空气流量为50 L/min时,火焰吹熄极限从约0.7扩宽到约0.3,且NH3/空气当量比为0.40~0.55时,等离子体辅助氨燃烧的NO排放量可以下降到小于100 mg/m3。Kim等人[17]研究了介质阻挡放电等离子体对NH3/空气预混火焰的稳定性及NOx排放特性的影响,研究结果表明,添加等离子体能更有效地稳定火焰和扩大吹熄极限,并且在NH3/空气当量比为1.0时,有等离子体助燃下的NOx排放量比无等离子体助燃时降低了约320 mg/m3
综上可知,甲烷助燃和等离子体助燃均可显著提高氨火焰的稳定性,并扩展其吹熄极限。然而,现有研究中尚无将这2种助燃方式相结合,对其助燃效果进行对比分析的工作。此外,不同助燃方式对氨燃料旋流火焰的燃烧特性及NOx排放特性的影响不够明确。为此,本文在自主研发的一种滑动电弧等离子体发生器与旋流燃烧器相结合的燃烧装置中进行了NH3/CH4/空气燃烧的实验研究,开展了旋流火焰结构拍摄、燃烧稳定域测量、光谱强度诊断、火焰温度测量、尾气排放分析的工作。揭示不同助燃方式(甲烷助燃和等离子体助燃以及等离子体耦合甲烷助燃)对氨燃烧特性及污染物排放特性的影响,以期为实现氨燃料的清洁高效燃烧提供实验依据。
本文设计了一套滑动电弧等离子体发生器与旋流燃烧器相耦合来辅助氨燃烧的实验装置,其示意如图1所示。实验装置由等离子体发生器、旋流燃烧器、高频高压电源、供气系统和测量诊断系统组成。等离子体发生器是由内置棒状高压电极、接地电极和旋流气环1构成。旋流燃烧器则是由电弧喷嘴、圆柱形石英管以及旋流气环2构成。燃烧器的旋流强度用旋流数S来表征,S由电弧喷嘴与旋流气环2的几何结构决定,其定义式为:
S=23[1(Di/Do)3][1(Di/Do)2]tanθ
式中:DoDi分别为旋流气环2和电弧喷嘴的外径,mm;θ为旋流器的叶片倾斜角度,°;旋流数S是一个无量纲参数。本文中,Do=23.4 mm,Di=8 mm,θ =30°,代入式(1)中计算得出该燃烧器的旋流数S为0.42。
实验过程中通过质量流量计来控制所需气体流量,包括空气、氨气和甲烷,其测量精度为±1%。燃烧火焰图像使用一台数码相机(佳能EOS 60D)拍摄,实验过程中,感光度(ISO=100),曝光时间为1/8 s。采用2种测温方式相组合的方式来测量火焰与电弧喷嘴处轴向距离的火焰温度:1)轴向距离5 mm处的温度从OH谱线拟合中获得;2)使用B型热电偶得到轴向距离为25、65、105、165、 225 mm的火焰温度。采用8通道光纤光谱仪(AvaSpec-2048,光强测量精度±0.5%FS,光学分辨率0.1 nm,FS表示的是满量程)在旋流燃烧器喷嘴上方5 mm处测得等离子体助燃产生的发射光谱,波长测量范围为200~900 nm。采用烟气分析仪(HORIBA,MEXA-584L,分辨率0.1 mg/m3)测量燃烧器出口的废气成分,包括NO(测量精度±1%FS)和O2(测量精度±0.1%FS)。
为对比等离子体助燃、甲烷助燃以及等离子体耦合甲烷助燃对NH3旋流火焰燃烧特性及NO生成特性的影响,本文设计了6种不同的助燃方式。需要指出的是,本文中等离子体放电功率最大设置为1 kW,这是基于前期实验过程中氨助燃效果及等离子体放电稳定性确定的,而甲烷的流量是依据甲烷能够稳定助燃氨燃烧时所需要的流量确定的。在本文中,甲烷流量最大值设定为5 L/min,并且各种工况下甲烷燃烧所需要的空气量均为理想当量比φ =1.0下所对应的流量,不随氨燃烧的当量比发生变化而改变,如无特殊说明,本文中的当量比均为氨燃烧所对应的当量比。此外,考虑等离子体放电及氨燃烧的稳定性,NH3所需的空气流量固定为25 L/min。
实验中,6种助燃方式见表1,具体如下。
甲烷助燃(Case1) 空气和甲烷通过旋流气环1进入实验装置,氨气由旋流气环2供给,点火方式采用1 kW滑动电弧等离子体,放电时间为3 s。
等离子体耦合甲烷助燃(Case2—Case5)  空气和甲烷同样由旋流气环1进入,氨气通过旋流气环2供给,等离子体放电在点火结束后持续存在。在这4种工况中,等离子体功率从0.2 kW逐步增加至0.8 kW,CH4流量相应由4 L/min减至1 L/min。
等离子体助燃(Case 6) 仅采用等离子体作为助燃手段,空气由旋流气环1、氨气由旋流气环2喷入,等离子体放电在点火结束后持续存在。
图2展示了甲烷助燃、等离子体耦合甲烷助燃以及等离子体助燃下的氨燃烧火焰图像随当量比的变化。由图2a)可见,当量比为0时表示只有甲烷燃烧而没有氨燃烧,此时火焰呈现蓝色,主要是CH*光谱发射带引起的[18]。随着当量比的进一步增加(φ=0.2~0.8),可以观察到火焰由先前的蓝色火焰转变为橙蓝相间火焰,橙色主要来源于氨燃烧分解时产生NH2*光谱发光产生颜色[19]。当量比为1.0~1.2时的火焰颜色逐渐变为以橙色为主,其颜色明亮强度随着当量比增加而增强。对于火焰形态而言,随着当量比的增加(φ=0~1.2),火焰长度逐渐拉长,当φ=1.2时,火焰长度最长,并且随着当量比的进一步增加时,火焰快速熄灭。
为了说明等离子体耦合甲烷助燃下的氨火焰燃烧特性,图2b)—图2e)展示了4种不同工况下的氨火焰图像。与图2a)相比,当甲烷耦合等离子体助燃时,氨火焰稳定燃烧的当量比由0~1.2显著扩展到0~2.0。由图2b)可见,当量比为1.6~2.0时,在滑动电弧放电周围形成了微弱火焰,大部分氨气未燃尽,而当等离子体耦合甲烷助燃中等离子体助燃的比例进一步提升时,即Case3—Case5工况(图2c)—图2e)),不仅火焰的亮度得到了明显提升,而且在φ=1.6~2.0,氨火焰性能得到了显著提升。因此,与甲烷助燃相比,等离子体耦合甲烷助燃下的氨火焰亮度明显提升,燃烧极限显著增加。图2f)进一步展示了等离子体助燃下的氨燃烧火焰图像,在φ≤1.2时,随着当量比的增加,也就是氨气流量的增加,火焰高度逐渐升高。然而,当量比进一步增加时,火焰结构并未明显改变。此外,通过图2a)—图2f)对比还可发现,相比于Case1—Case4,Case5和Case6工况下氨燃烧的火焰明亮强度更强,火焰长度在相同的当量比下更短,这表明此工况下的氨燃烧速度更快,并快速燃尽。
综上所述,相比于单纯的甲烷助燃Case1,等离子体耦合甲烷助燃Case2—Case5和等离子体助燃Case6既能明显地扩展氨燃烧极限,又能提升火焰发光强度,这表明等离子体助燃是一种有效的氨助燃手段。
图3展示了在甲烷助燃和等离子体助燃下的氨燃烧火焰稳定域。由图3a)可见,当甲烷助燃时,甲烷流量从1 L/min增加到5 L/min时,氨火焰稳定燃烧的当量比由0.6~0.8显著扩展到了0~1.2。因此,甲烷助燃时,增加一定的甲烷可以有效增加氨燃烧火焰稳定性。相比于图3a)下的甲烷助燃,图3b)等离子体助燃对提升氨燃烧稳定域的拓展更加有效,当等离子体放电为1 kW时,氨燃烧的稳定域拓展为0.1~5.0。
图4展示了甲烷助燃Case1、等离子体助燃Case6和等离子体耦合甲烷助燃Case2—Case5工况下的氨燃烧火焰稳定域。由图4可见,Case2(等离子体功率0.2 kW、甲烷4 L/min)和Case3(等离子体功率0.4 kW、甲烷3 L/min)使得氨火焰稳定燃烧的当量比均为0~5.0。然而,图3中甲烷流量为4、3 L/min助燃氨的稳定燃烧当量比分别为0.1~1.0和0.2~0.9;等离子体功率为0.2、0.4 kW助燃氨的稳定燃烧当量比分别为1.4~4.0和0.5~5.0。因此,与只有甲烷助燃相比,等离子体耦合甲烷助燃可以有效地增加氨燃烧火焰稳定性。
等离子体放电产生的活性物质对氨燃烧具有重要作用,为了进一步探讨等离子体耦合甲烷助燃Case4—Case5和等离子体助燃Case6对氨燃烧的助燃效果,图5展示了纯空气放电和不同助燃方式下等离子体放电产生的发射光谱。由图5a)可见,纯空气等离子体放电发射谱主要由NO(220~300 nm)、OH(308 nm)、O(777 nm和844 nm)和Cr的原子光谱组成。与之相比,Case4(图5b))发射光谱出现新的活性物质,如NH(336 nm)、CN(388 nm)、CH(431 nm)和Hα(656 nm)。Case5(图5c))的发射光谱各种活性粒子的强度都比Case4的更强,表明Case5能够进一步提升氨燃烧性能。与纯空气放电相比,当添加NH3后,Case6(图5d))的发射光谱有较为明显的变化,OH和O的强度也显著增强,并且出现了新的NH、Hα活性粒子。此外,与Case6相比,Case5的OH和Hα谱线强度显著增强,但是O谱线强度有所下降。这表明等离子体助燃Case6和等离子体耦合甲烷助燃Case5下的活性粒子较多,能够有效地增强等离子体助燃中的化学效应。
电子密度Ne是确定等离子体电离率及电子碰撞反应的关键参数,可以通过Hα谱线的斯塔克展宽方法来获得[20]图6展示了Hα谱线按照Voigt函数进行拟合的实验曲线。谱线的洛伦兹展宽的半高宽为0.073 nm,斯塔克展宽约为0.061 nm,Ne约为1.63×1020 m–3图7进一步展示了不同助燃方式下等离子体中电子数密度随当量比的变化。各种助燃方式下的电子数密度都随着当量比的增加而增加,并且等离子体助燃Case6的电子数密度比等离子体耦合甲烷助燃Case4—Case5的高,这是由于等离子体放电功率增加会导致电子数密度增大[21]
图8展示了在不同助燃方式下OH(308 nm)、O(777 nm)、Hα(656 nm)、NH(336 nm)活性物质产生的光谱强度随当量比的变化。在固定助燃方式下,活性物质OH(308 nm)、O(777 nm)和NH(336 nm)强度随当量比缓慢增加,而Hα(656 nm)的强度对当量比特别敏感,在更高的当量比下会获得更多的Hα(656 nm)。由图8a)、图8b)发现,相比于等离子体助燃Case6和等离子体耦合甲烷助燃Case4,等离子体耦合甲烷助燃Case5的Hα (656 nm)、OH(308 nm)光谱辐射强度更大。这是因为Case5相比与Case6的燃料里存在甲烷,并且比Case4有更多的电子数密度。Case5主要是通过CH4分子或离子与高能电子或激发态N2*之间的碰撞来产生更多的H,反应式[22]为:
CH4+eCH3+H+e
CH4++eCH3+H
CH4+N2*CH3+H+N2
此外,Case5会产生更多的H2O[22-23],氧或高能电子与水的碰撞和活性粒子H与氧的碰撞都会更有效地形成OH,具体反应式为:
O(1D)+H2O2OH
e+H2OOH+H+e
O+H2OH+H
H+O2OH+O
H+O(+M)OH(+M)
式中:M表示第三体,在化学反应中不参与净反应,但能通过碰撞吸收或提供能量,从而影响反应速率的任何分子或原子,其作用是维持系统的能量守恒。
因此,等离子体耦合甲烷助燃Case5产生了比等离子体助燃Case6和等离子体耦合甲烷助燃Case4更多的OH和H,从而显著加快了NH3氧化过程中的链式分支反应。
等离子体助燃Case6的辐射强度比等离子体耦合甲烷助燃Case4—Case5的辐射强度强(图8c)、图8d))。因为相比于Case4和Case5而言,从尾气分析中测得的O2可知,Case6在燃烧过程中消耗氧气较慢,并且电子数密度较高。使得产生O自由基的反应路径增强,主要反应为高能电子与O2直接碰撞反应和激发态N2*与O2反应[24]
e+O2e+2O
N2*+O2N2+2O
Case4—Case6产生NH的主要途径是高能电子与基态NH3的碰撞[25],反应为:
e(3.9eV)+NH3NH+H2+e
e(8.6eV)+NH3NH+2H+e
由于Case6的电子数密度比Case4和Case5高,因此产生了更多的NH。
总体而言,等离子体耦合甲烷助燃Case5产生了比等离子体助燃Case6和等离子体耦合甲烷助燃Case4更多的活性物质OH和H,同时加速了氨燃料与O2的反应速率,改善了NH3的燃烧特性。
在氨燃烧机理研究中,温度分布的精确表征对于深入探究其燃烧热效应特性具有核心评价作用。图9展示了Case5等离子体耦合甲烷助燃φ=0.8时,OH谱线拟合下的气体温度。由图9可见,经实验值与模拟值拟合得到气体温度为4 200 K,表明等离子体射流区域的温度较高。图10为Case4—Case6工况下等离子体射流区域气体温度随当量比变化(距燃烧器喷嘴5 mm处)。由图10可见,在当量比为0.6时,等离子体耦合甲烷助燃Case5的温度要高于Case4和等离子体助燃Case6的温度。在当量比为0.8~1.4时,Case5工况下烟气最高温度达到了4 200 K,而Case6工况下烟气温度进一步上升至4 350 K。
图11展示了当量比在0.6~1.2时不同助燃方式下的氨燃烧火焰温度随轴向距离和当量比的变化。由图11可见,氨火焰温度随轴向距离的增加而降低。在固定的助燃方式下,火焰轴向最高温度随着当量比的增加呈现先升高后降低的变化趋势,在当量比为0.8左右时,火焰温度达到最大值,在Case6工况下的火焰温度可达2 030 K左右。当量比为0.6时,等离子体耦合甲烷助燃Case5工况的火焰温度最高,根据2.2节中光谱诊断结果,可能与此工况下生成了大量的OH、H自由基有关,由OH自由基引发反应(式(14)、式(15))对热释放有显著的促进作用[26]
NH3+OHNH2+H2O
NH2+OHNH+H2O
这些自由基在NH3燃烧的过程中都起着重要作用,有利于提高燃料燃烧反应速率。此外,在当量比为0.6,从整体温度分布来看,等离子体耦合甲烷助燃Case2和Case3的火焰温度比较低,可能是由于此时等离子体功率比较低,产生的活性基团较少,等离子体助燃下的化学效应减弱,导致火焰温度较低。当当量比分别为0.8、1.0和1.2时的氨火焰温度随着轴向距离的增加,Case6工况下氨燃烧的火焰温度最高,火焰最高温度相较于Case1工况的氨燃烧高21.8%左右,但比Case5工况下的温度仅高出100 K左右。总之,Case5和case6工况对提升氨的燃烧性能比较有利。
NOx的生成量作为氨燃烧过程的核心表征参数,是评估氨燃烧清洁性的重要指标。图12展示了不同助燃方式下氨燃烧尾气中NO排放质量浓度和O2体积分数随着当量比的变化规律。由图12a)可见,不同助燃工况下NO排放质量浓度都随着当量比的增加表现出先上升后下降的变化趋势,最大NO质量浓度对应的当量比为0.6左右,当量比进一步增加时,NO排放量显著减少,在φ=2.0时基本可以实现5 mg/m3的相对较低的NO排放量。当量比φ=0时,即未向燃烧器添加氨燃料时,纯甲烷燃烧产生的NO几乎为0,而添加了等离子体的甲烷燃烧尾气NO质量浓度在855~4 000 mg/m3,这表明热态NO是在空气中形成的,滑动电弧的应用增加了纯甲烷火焰的NO排放量。在类似的等离子体辅助甲烷燃烧火焰研究中,Choe[27]和Wookyung[28]等人发现纳秒脉冲等离子体会显著增加NOx排放量,这和本研究的实验结果是相符合的。对于不添加氨的甲烷旋流火焰,应用滑动电弧后NO排放量升高的原因可能是火焰温度的升高。在氨燃烧热效应分析中可知,采用OH谱线拟合获得等离子体射流区火焰温度可达3 000 K以上,高温会促进热力型NO的生成[29],因此滑动电弧作用下会导致尾气中NO排放量的增加。
一旦当量比大于零(φ>0),即向燃烧器添加氨燃料时,除了热力型NO外,燃烧火焰中还会生成燃料型NO。在0<φ≤0.6条件下,各种助燃工况下的氨燃烧尾气NO质量浓度都随着当量比的增加而显著上升,基本都达到3 000~7 000 mg/m3。这主要是因为此时存在大量的O、OH自由基,N、NH、NH2与其反应形成HNO从而产生NO[30]。HNO、NH和N都是NO形成的原因,但是HNO对NO形成的贡献为70%,而N自由基对NO生成的贡献为10%~15%[31]。上述主要反应路径为:
NH2+OHNO+H
NH+OHHNO+H
HNO+OHNO+H2O
但在此当量比条件下,相比于甲烷助燃Case1和等离子体助燃Case6的氨燃烧,等离子体耦合甲烷助燃Case3—Case5氨燃烧尾气NO排放量更高。可能是因为燃烧火焰中存在大量的HCN,O、OH等自由基可将HCN转化为NO[32],导致NO排放增加。
φ>0.6时,NO质量浓度随着当量比的提高开始呈现显著降低的趋势。这可能是因为HNO生成量减少,导致由N、NH、NH2氧化反应产生的NO含量降低。并且在富燃条件下,N、NH与NH2会与NO直接反应,导致由该类自由基生成的NO质量浓度进一步降低。主要消耗NO反应路径为[33]
NH2+NON2+H2O
NH+NON2+OH
此外,相对于应用了等离子体助燃的工况来说,等离子体区域会形成大量的HO2来消耗NO[34]。存在如下反应路径来减少NO排放:
NO+HO2OH+NO2
NO2+HO2HONO+O2
更为值得注意的是,当量比为0.8~1.2时,相较于甲烷助燃Case1和等离子体助燃Case6的氨燃烧,等离子体耦合甲烷助燃Case5的NO质量浓度最低,可达到100 mg/m3以下。这可能是两方面原因造成的,一方面,Case5产生了比Case1更多的NH2、NH自由基,增强了NH2、NH还原NO的化学反应,从而降低了NO排放量[35];另一方面,Case6的等离子体射流区温度最高,产生了更多的热力型NO,因此其NO排放量也相对较高。当量比为1.4~2.0时,Case2的NO质量浓度又上升至1 000 mg/m3左右。
图12b)可见,尾气中的O2体积分数进一步反映了氨燃烧特性。当量比从0增加到约0.6~0.8的过程中,O2体积分数几乎呈线性下降。等离子体耦合甲烷助燃Case5的O2体积分数低于等离子体助燃Case6的。此外,在φ<0.6时,相比于甲烷助燃Case1,等离子体耦合甲烷助燃Case2条件下氨燃烧的O2消耗更快。但是,当量比进一步增加时,Case2的氨火焰尾气中O2体积分数会比较高,特别是在当量比为1.6~2.0下,氨火焰尾气中O2体积分数达到了16%左右,这是由于此时大部分氨气未燃尽。
在与高频交流电驱动的旋转滑动电弧等离子体放电装置相耦合的旋流燃烧器上进行了氨燃烧的实验研究,研究甲烷助燃Case1和等离子体助燃Case6以及等离子体耦合甲烷助燃Case2—Case5对氨燃烧特性及污染物排放特性的影响。从实验结果中得出主要结论如下。
1)等离子体耦合甲烷助燃Case2—Case5以及等离子体助燃Case6都可以有效地改善氨的燃烧特性,扩展稳燃极限范围。与甲烷助燃Case1当量比为0~1.2的稳燃范围相比,Case2—Case6的氨燃烧稳燃极限范围均可扩展到当量比为0~5.0。
2)在施加了等离子体条件下,与纯空气放电相比,添加氨燃料会产生新的NH和Hα谱线,并且OH、O自由基含量会显著增强。相比于等离子体助燃Case6,等离子体耦合甲烷助燃Case5不仅生成新的活性物质CH、CN,而且产生了更多的OH、H自由基,从而增强了等离子体助燃中的化学效应。
3)相比于甲烷助燃Case1,等离子体耦合甲烷助燃Case5以及等离子体助燃Case6都可以更加有效地提升氨火焰温度。在φ=0.6时,Case5的火焰温度最高,可达2 030 K左右,φ=0.8~1.2时,Case5的火焰温度仅比Case6低100 K左右。
4)在φ=0~0.6的条件下,各种助燃方式下的氨燃烧NO排放质量浓度都在3 000~7 000 mg/m3。然而,当φ=0.8~2.0时,等离子体耦合甲烷助燃Case5是降低氨燃烧尾气NO排放的最佳方式。在φ=0.6增加到φ=0.8时,NO排放质量浓度从超过7 000 mg/m3快速降低至100 mg/m3以下。
  • 国家重点研发计划项目(2023YFB4005705; 2023YFB4005702-03)
  • 国家自然科学基金项目(52207151)
  • 合肥综合性国家科学中心能源研究院(安徽省能源实验室)自主立项项目(22KZZ525; 23KZS402; 22KZS301; 22KZS304)
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2025年第54卷第8期
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doi: 10.19666/j.rlfd.202505093
  • 接收时间:2025-06-06
  • 首发时间:2026-03-05
  • 出版时间:2025-08-25
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  • 收稿日期:2025-06-06
基金
National Key Research and Development Program(2023YFB4005705; 2023YFB4005702-03)
国家重点研发计划项目(2023YFB4005705; 2023YFB4005702-03)
National Natural Science Foundation of China(52207151)
国家自然科学基金项目(52207151)
Self-initiated Project of Institute of Energy, Hefei Comprehensive National Science Center (Anhui Provincial Energy Laboratory)(22KZZ525; 23KZS402; 22KZS301; 22KZS304)
合肥综合性国家科学中心能源研究院(安徽省能源实验室)自主立项项目(22KZZ525; 23KZS402; 22KZS301; 22KZS304)
作者信息
    1.安徽工业大学能源与环境学院,安徽 马鞍山 243002
    2.合肥综合性国家科学中心能源研究院(安徽省能源实验室),安徽 合肥 230031
    3.安徽理工大学地球与环境学院,安徽 淮南 232001
    4.中国科学院合肥物质科学研究院等离子体物理研究所,安徽 合肥 230031

通讯作者:

林启富(1987),男,博士,副研究员,主要研究方向为低温等离子体物理、等离子体助燃、氢氨能应用,
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2种不同金属材料的力学参数

Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)

Genus
种数
Number of
species
占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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