氨/甲烷扩散火焰中OH*、NH2*和NH*光谱辐射特性研究

doi:10.11949/0438-1157.20230989

摘要/Abstract

摘要：

基于火焰光谱诊断平台，利用光谱成像系统获得氨/甲烷扩散火焰的OH*、NH₂*和NH*辐射分布，并结合CHEMKIN探究其反应机理。结果表明：与纯甲烷燃烧相比，氨掺混后火焰的OH*辐射分布区域和辐射强度均降低较明显，在火焰下游分布形态向外延展。随着氨掺混比例的增加，NH₂*辐射分布区域向火焰下游拉升，辐射强度增加。NH*辐射分布区域基本不变，辐射强度随氨掺混比例的增加先增加后降低，在氨分数为0.2~0.3时达到最大。三个自由基辐射强度均随当量比增大而增加，其中OH*分布偏向氧化剂侧，NH₂*和NH*偏向燃料侧。添加NH₂*和NH*反应机理后，模拟结果显示，NH₂*的主要来源为氨的脱氢过程，掺氨比例的变化直接影响NH₂*的生成，NH*最大生成反应的反应生成率受氨和甲烷混合比例的影响。

关键词: 氨, 甲烷, 扩散, 自由基, 光谱辐射

Abstract:

Based on the flame spectroscopy diagnostic platform, a spectral imaging system was utilized to obtain the OH*, NH₂* and NH* radiation distributions of the ammonia/methane diffusion flame. The reaction mechanism was explored in the CHEMKIN. The results show that compared with pure methane combustion, the OH* radiation distribution zone and radiation intensity of the flame after ammonia blending are significantly reduced, and the distribution pattern extends outwards downstream of the flame. With the increase of ammonia blending ratio, the radiation distribution zone of NH₂* was raised to the downstream of the flame, and the radiation intensity increased. NH* radiation distribution zone was basically unchanged. The radiation intensity of NH* increased and then decreased with the increase of ammonia blending ratio. NH* radiation intensity reached the maximum when the ammonia fraction was from 0.2 to 0.3. The radiative intensity of the three radicals increased with the equivalence ratios, in which the distribution of OH* was biased toward the oxidant side, while NH₂* and NH* were biased toward the fuel side. With the addition of NH₂* and NH* reaction mechanisms, the simulation show that the main source of NH₂* was the dehydrogenation process of ammonia. The changes in the ammonia blending ratio directly affected the generation of NH₂*. The maximum production reaction of NH* indicated that the rate of the reaction generation of NH* was affected by the mixing ratio of ammonia and methane.

Key words: ammonia, methane, diffused, radicals, spectral radiation

中图分类号:

O 433.52

段正巧, 龚岩, 郭庆华, 于广锁. 氨/甲烷扩散火焰中OH*、NH₂*和NH*光谱辐射特性研究[J]. 化工学报, 2023, 74(11): 4710-4719.

Zhengqiao DUAN, Yan GONG, Qinghua GUO, Guangsuo YU. Spectral radiation characterization of OH*, NH₂* and NH* in ammonia/methane diffusion flame[J]. CIESC Journal, 2023, 74(11): 4710-4719.

图/表 14

图1 火焰化学发光检测平台

Fig.1 Flame chemiluminescence detection platform

表1 实验工况

Table 1 Experimental conditions

序号	CH₄/(L·min^-1)	NH₃/(L·min^-1)	$X N H 3$	O₂/(L·min^-1)	φ
1	0.30	0	0	0.60	1.0
2	0.27	0.03	0.1	0.34~0.84	0.6~1.5
3	0.24	0.06	0.2	0.32~0.79	0.6~1.5
4	0.21	0.09	0.3	0.29~0.73	0.6~1.5
5	0.18	0.12	0.4	0.27~0.68	0.6~1.5
6	0.15	0.15	0.5	0.25~0.62	0.6~1.5

表1 实验工况

Table 1 Experimental conditions

序号	CH₄/(L·min^-1)	NH₃/(L·min^-1)	$X N H 3$	O₂/(L·min^-1)	φ
1	0.30	0	0	0.60	1.0
2	0.27	0.03	0.1	0.34~0.84	0.6~1.5
3	0.24	0.06	0.2	0.32~0.79	0.6~1.5
4	0.21	0.09	0.3	0.29~0.73	0.6~1.5
5	0.18	0.12	0.4	0.27~0.68	0.6~1.5
6	0.15	0.15	0.5	0.25~0.62	0.6~1.5

图2 氨/甲烷混合扩散火焰自发辐射光谱曲线

Fig.2 Ammonia/methane diffusion flame photometry graph

表2 NH2*、NH*基元反应

Table 2 NH2*， NH* radical reactions

序号	NH₂*	序号	NH*
R1	NH₂* $̿$ NH₂+hv	R11	NH* $̿$ NH+hv
R2	NH₂*+M $̿$ NH₂+M	R12	NH*+NH₃ $̿$ NH+NH₃
R3	NH+H+M $̿$ NH₂*+M N₂/1.0/NH₃/2.5/AR/0.38/HE/0.36/CH₄/0.76/CO/1.16/H₂/1.14/	R13	NH*+M $̿$ NH+M O₂/1.0/NH₃/0.0/H₂O/5.3/C₂H₆/4.2/CH₄/2.3/CO/2.2/H₂/1.5/N₂/0.02/
R4	NH₂*+H₂ $̿$ NH₃+H	R14	NH*+H₂O $̿$ NH₂+OH
R5	NH+H₂ $̿$ NH₂+H	R15	NH*+H₂ $̿$ NH₂+H
R6	NH₂*+H₂O $̿$ NH₃+OH	R16	NH*+NH₃ $̿$ 2NH₂
R7	N₂+NH₂*+H $̿$ N₂(A)+NH₃	R17	NH*+H $̿$ N+H₂
R8	NH₂+N₂(A) $̿$ NH₂*+N₂	R18	N₂(A)+NH $̿$ N₂+NH*
R9	N₂H₄+H $̿$ NH₃+NH₂*	R19	CH+NO $̿$ NH*+CO
R10	N₂H₄+H $̿$ N₂H₃+H₂

表2 NH2*、NH*基元反应

Table 2 NH2*， NH* radical reactions

序号	NH₂*	序号	NH*
R1	NH₂* $̿$ NH₂+hv	R11	NH* $̿$ NH+hv
R2	NH₂*+M $̿$ NH₂+M	R12	NH*+NH₃ $̿$ NH+NH₃
R3	NH+H+M $̿$ NH₂*+M N₂/1.0/NH₃/2.5/AR/0.38/HE/0.36/CH₄/0.76/CO/1.16/H₂/1.14/	R13	NH*+M $̿$ NH+M O₂/1.0/NH₃/0.0/H₂O/5.3/C₂H₆/4.2/CH₄/2.3/CO/2.2/H₂/1.5/N₂/0.02/
R4	NH₂*+H₂ $̿$ NH₃+H	R14	NH*+H₂O $̿$ NH₂+OH
R5	NH+H₂ $̿$ NH₂+H	R15	NH*+H₂ $̿$ NH₂+H
R6	NH₂*+H₂O $̿$ NH₃+OH	R16	NH*+NH₃ $̿$ 2NH₂
R7	N₂+NH₂*+H $̿$ N₂(A)+NH₃	R17	NH*+H $̿$ N+H₂
R8	NH₂+N₂(A) $̿$ NH₂*+N₂	R18	N₂(A)+NH $̿$ N₂+NH*
R9	N₂H₄+H $̿$ NH₃+NH₂*	R19	CH+NO $̿$ NH*+CO
R10	N₂H₄+H $̿$ N₂H₃+H₂

图3 NH2*和NH*辐射强度与模拟摩尔分数积分值

Fig.3 NH2*, NH* radiation intensity and simulated mole fraction integration values

图4 氨/甲烷混合扩散火焰图像

Fig.4 Ammonia/methane diffusion flame image

图5 氨/甲烷不同混合比OH*相对辐射强度分布

Fig.5 OH* relative radiation intensity distribution of ammonia/methane flames with different mixing ratios

图6 氨/甲烷不同混合比NH2*相对辐射强度分布

Fig.6 NH2* relative radiation intensity distribution of ammonia/methane flames with different mixing ratios

图7 氨/甲烷不同混合比NH*相对辐射强度分布

Fig.7 NH* relative radiation intensity distribution of ammonia/methane flames with different mixing ratios

图8 不同当量比OH*、NH2*、NH*相对峰值强度

Fig.8 Relative peak intensity of OH*, NH2* and NH* at different equivalent ratios

图9 OH*与NH2*和NH*辐射区域相对位置(XNH3=0.1，φ=1.0)

Fig.9 Relative position of OH*, NH2* and NH*(XNH3= 0.1, φ = 1.0)

图10 OH*、NH2*和OH*峰值位置随氨掺混比的变化

Fig.10 OH*, NH2* and NH* peak radiation intensity positions with various ammonia mixing ratio

图11 掺氨比例为0.1时NH2*、NH*反应生成率

Fig.11 NH2*, NH* reaction production rate at ammonia mixing ratio of 0.1

图12 NH*反应生成率积分

Fig.12 NH* reaction production rate integral

参考文献 35

1	Valera-Medina A, Xiao H, Owen-Jones M, et al. Ammonia for power[J]. Progress in Energy and Combustion Science, 2018, 69: 63-102.
2	Kobayashi H, Hayakawa A, Somarathne K D K A, et al. Science and technology of ammonia combustion[J]. Proceedings of the Combustion Institute, 2019, 37(1): 109-133.
3	Reiter A J, Kong S C. Combustion and emissions characteristics of compression-ignition engine using dual ammonia-diesel fuel[J]. Fuel, 2011, 90(1): 87-97.
4	Han X L, Wang Z H, Costa M, et al. Experimental and kinetic modeling study of laminar burning velocities of NH₃/air, NH₃/H₂/air, NH₃/CO/air and NH₃/CH₄/air premixed flames[J]. Combustion and Flame, 2019, 206: 214-226.
5	周上坤, 杨文俊, 谭厚章, 等. 氨燃烧研究进展[J]. 中国电机工程学报, 2021, 41(12): 4164-4182.
	Zhou S K, Yang W J, Tan H Z, et al. Research progress of ammonia combustion[J]. Proceedings of the CSEE, 2021, 41(12): 4164-4182.
6	Ballester J, García-Armingol T. Diagnostic techniques for the monitoring and control of practical flames[J]. Progress in Energy and Combustion Science, 2010, 36(4): 375-411.
7	周莹, 白永辉, 宋旭东, 等. 自由基的化学发光特性在火焰光谱诊断的应用综述[J]. 光谱学与光谱分析, 2020, 40(11): 3358-3364.
	Zhou Y, Bai Y H, Song X D, et al. Application of chemiluminescence in spectral diagnosis: a review[J]. Spectroscopy and Spectral Analysis, 2020, 40(11): 3358-3364.
8	闫帅, 杨家宝, 龚岩, 等. CO₂稀释对甲烷反扩散火焰结构的影响研究[J]. 化工学报, 2022, 73(3): 1335-1342.
	Yan S, Yang J B, Gong Y, et al. Effects of CO₂ dilution on the structure of methane inverse diffusion flame[J]. CIESC Journal, 2022, 73(3): 1335-1342.
9	Baumgardner M E, Harvey J. Analyzing OH, CH, and C₂* chemiluminescence of bifurcating FREI propane-air flames in a micro flow reactor[J]. Combustion and Flame, 2020, 221: 349-351.
10	Hardalupas Y, Panoutsos C S, Taylor A M K P. Spatial resolution of a chemiluminescence sensor for local heat-release rate and equivalence ratio measurements in a model gas turbine combustor[J]. Experiments in Fluids, 2010, 49(4): 883-909.
11	Bedard M J, Fuller T L, Sardeshmukh S, et al. Chemiluminescence as a diagnostic in studying combustion instability in a practical combustor[J]. Combustion and Flame, 2020, 213: 211-225.
12	Li Z S, Li B, Sun Z W, et al. Turbulence and combustion interaction: high resolution local flame front structure visualization using simultaneous single-shot PLIF imaging of CH, OH, and CH₂O in a piloted premixed jet flame[J]. Combustion and Flame, 2010, 157(6): 1087-1096.
13	Walsh K T, Fielding J, Smooke M D, et al. A comparison of computational and experimental lift-off heights of coflow laminar diffusion flames[J]. Proceedings of the Combustion Institute, 2005, 30(1): 357-365.
14	Wang Z Y, Sunderland P B, Axelbaum R L. Double blue zones in inverse and normal laminar jet diffusion flames[J]. Combustion and Flame, 2020, 211: 253-259.
15	Zhu X R, Khateeb A A, Roberts W L, et al. Chemiluminescence signature of premixed ammonia-methane-air flames[J]. Combustion and Flame, 2021, 231: 111508.
16	Vigueras-Zúñiga M O, Tejeda-del-Cueto M E, Mashruk S, et al. Methane/ammonia radical formation during high temperature reactions in swirl burners[J]. Energies, 2021, 14(20):6624.
17	Pugh D, Runyon J, Bowen P, et al. An investigation of ammonia primary flame combustor concepts for emissions reduction with OH, NH₂ and NH* chemiluminescence at elevated conditions[J]. Proceedings of the Combustion Institute, 2021, 38(4): 6451-6459.
18	Choe J, Sun W T. Experimental investigation of non-equilibrium plasma-assisted ammonia flames using NH₂* chemiluminescence and OH planar laser-induced fluorescence[J]. Proceedings of the Combustion Institute, 2023, 39(4): 5439-5446.
19	Zhu X R, Khateeb A A, Guiberti T F, et al. NO and OH* emission characteristics of very-lean to stoichiometric ammonia-hydrogen-air swirl flames[J]. Proceedings of the Combustion Institute, 2021, 38(4): 5155-5162.
20	Miao J, Leung C W, Cheung C S, et al. Effect of H₂ addition on OH distribution of LPG/air circumferential inverse diffusion flame[J]. International Journal of Hydrogen Energy, 2016, 41(22): 9653-9663.
21	Ren F, Cheng X G, Gao Z, et al. Effects of NH₃ addition on polycyclic aromatic hydrocarbon and soot formation in C₂H₄ co-flow diffusion flames[J]. Combustion and Flame, 2022, 241: 111958.
22	毛晨林, 王平, Prashant Shrotriya, 等. 含氨燃料预混火焰的层流火焰速度及NO排放特性[J]. 化工学报, 2021, 72(10): 5330-5343.
	Mao C L, Wang P, Shrotriya P, et al. Laminar flame speed and NO emission characteristics of premixed flames with different ammonia-containing fuels[J]. CIESC Journal, 2021, 72(10): 5330-5343.
23	Li N N, Deng H X, Xu Z Z, et al. Experimental study on NH₃/H₂/air, NH₃/CO/air, NH₃/H₂/CO/air premix combustion in a closed pipe and dynamic simulation at high temperature and pressure[J]. International Journal of Hydrogen Energy, 2023, 48(88): 34551-34564.
24	Chen G Y, Zuo S S, Zhang J S, et al. Experimental and numerical simulation of effects of CO₂/N₂ concentration and initial temperature on combustion characteristics of biomass syngas[J]. Journal of Saudi Chemical Society, 2022, 26(4): 101490.
25	Mashruk S, Zitouni S E, Brequigny P, et al. Combustion performances of premixed ammonia/hydrogen/air laminar and swirling flames for a wide range of equivalence ratios[J]. International Journal of Hydrogen Energy, 2022, 47(97): 41170-41182.
26	Mashruk S, Zhu X R, Roberts W L, et al. Chemiluminescent footprint of premixed ammonia-methane-air swirling flames[J]. Proceedings of the Combustion Institute, 2023, 39(1): 1415-1423.
27	Guo Y, Shi H, Liu H, et al. Reactive molecular dynamics simulation and chemical kinetic modeling of ammonia/methane co-combustion[J]. Fuel, 2023, 354: 129341.
28	Füzesi D, Wang S Q, Józsa V, et al. Ammonia-methane combustion in a swirl burner: experimental analysis and numerical modeling with flamelet generated manifold model[J]. Fuel, 2023, 341: 127403.
29	Lesmana H, Zhu M M, Zhang Z Z, et al. Experimental and kinetic modelling studies of laminar flame speed in mixtures of partially dissociated NH₃ in air[J]. Fuel, 2020, 278: 118428.
30	Chen J D, Lubrano Lavadera M, Konnov A A. An experimental and modeling study on the laminar burning velocities of ammonia + oxygen + argon mixtures[J]. Combustion and Flame, 2023, 255: 112930.
31	Okafor E C, Naito Y, Colson S, et al. Experimental and numerical study of the laminar burning velocity of CH₄-NH₃-air premixed flames[J]. Combustion and Flame, 2018, 187: 185-198.
32	Konnov A A. An exploratory modelling study of chemiluminescence in ammonia-fuelled flames (Part 1)[J]. Combustion and Flame, 2023, 253: 112788.
33	Konnov A A. An exploratory modelling study of chemiluminescence in ammonia-fuelled flames (Part 2)[J]. Combustion and Flame, 2023, 253: 112789.
34	田鑫明, 杨家宝, 郭庆华, 等. 基于OH^*化学发光特性的CH₄/O₂扩散火焰燃料稀释效应研究[J]. 燃烧科学与技术, 2022, 28(3): 254-260.
	Tian X M, Yang J B, Guo Q H, et al. Fuel dilution effect based on OH^* chemiluminescence in CH₄/O₂ diffusion flame[J]. Journal of Combustion Science and Technology, 2022, 28(3): 254-260.
35	Yan S, Gong Y, Yang J B, et al. The effect of reaction mechanism on OH* chemiluminescence in methane inverse diffusion flame[J]. Fuel, 2023, 332: 126085.

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氨/甲烷扩散火焰中OH、NH₂和NH*光谱辐射特性研究

Spectral radiation characterization of OH, NH₂ and NH* in ammonia/methane diffusion flame

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