添加NH3对C2H4热解过程中烟灰颗粒及气态前体形成的影响

IF 5.8 2区工程技术 Q2 ENERGY & FUELS

Combustion and Flame Pub Date : 2025-07-05 DOI:10.1016/j.combustflame.2025.114324

Kai Zhang , Yishu Xu , Ronghao Yu , Jiahui Wu , Xiaobei Cheng

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引用次数: 0

摘要

在塞流反应器（PFR）中，在973 K-1373 K范围内对C2H4/NH3混合物进行热解。采用气相色谱（GC）和傅里叶变换红外（FTIR）对热解产物C2H4、NH3、C2H2、C6H6和HCN进行了定量分析，阐明了C2H4和NH3的热分解行为，以及NH3对气态烟尘前体形成的影响。结果表明，与单独热解相比，共热解过程中C2H4和NH3转化率均有所提高。C2H4对NH3分解的促进作用更为明显。动力学分析表明，C2H4 + NH2和NH3 + CH3反应分别是C2H4和NH3转化率提高的主要原因。NH3对碳烟前驱体（如C2H2和C6H6）形成的影响随反应温度的升高呈非单调趋势。在1273 K以下，NH3的加入促进了烟尘前驱体的形成，而在1273 K以上，NH3的加入抑制了烟尘前驱体的形成。这一趋势是由nh3诱导的C2H4分解增强和CN相互作用效应之间的竞争决定的。前者持续促进煤烟前驱体的形成，而后者仅在1273 K以上通过去除参与煤烟前驱体形成的C原子而显著抑制煤烟前驱体的形成。这一发现得到了FTIR测量的支持，在1273 K的温度下形成的HCN显著增加。值得注意的是，随着温度的进一步升高，HCN的浓度由于参与了含n多环芳烃（NPAHs）的形成而降低。有意义的是，采用气相色谱-质谱法（GC-MS）鉴定了NPAHs的分子结构。值得注意的是，现有的动力学机制无法令人满意地预测实验结果的定量趋势，这突出了进一步改进和完善机制的必要性。

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Effects of NH3 addition on soot particles and gaseous precursors formation in C2H4 pyrolysis

The pyrolysis of C₂H₄/NH₃ mixtures was conducted in a plug flow reactor (PFR) in the temperature range of 973 K-1373 K. The pyrolysis products, including C₂H₄, NH₃, C₂H₂, C₆H₆ and HCN, were quantified using gas chromatography (GC) and Fourier transform infrared (FTIR) spectroscopy to elucidate the thermal decomposition behavior of C₂H₄ and NH₃, as well as the effects of NH₃ on the formation of gaseous soot precursors. The results indicate that both C₂H₄ and NH₃ conversion increase during co-pyrolysis compared to their individual pyrolysis. Moreover, C₂H₄ shows a more pronounced promoting effect on NH₃ decomposition. Kinetic analysis reveals that the reactions C₂H₄ + NH₂ and NH₃ + CH₃ are primarily responsible for the increased conversion of C₂H₄ and NH₃, respectively. The effects of NH₃ on soot precursors formation (e.g., C₂H₂ and C₆H₆) exhibit a non-monotonic trend with reaction temperature. Specifically, NH₃ addition promotes soot precursors formation below 1273 K but inhibits it above 1273 K. This trend is determined by the competition between NH₃-induced enhancement of C₂H₄ decomposition and the effects of CN interactions. The former consistently promotes the formation of soot precursors, while the latter becomes significantly effective in inhibiting their formation only above 1273 K by removing C atoms from participating in soot precursors formation. This finding is supported by FTIR measurements with a significant increase of HCN being formed at temperature at 1273 K. It should be noted that as the temperature further increases, the concentration of HCN decreases due to its involvement in the formation of N-containing polycyclic aromatic hydrocarbons (NPAHs). Meaningfully, the molecular structure of NPAHs were identified using gas chromatography-mass spectrometry (GC–MS). Notably, existing kinetic mechanisms are unable to satisfactorily predict the quantitative trends of the experimental results, highlighting the need for further mechanism improvement and refinement.

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来源期刊

Combustion and Flame 工程技术-工程：化工

CiteScore

9.50

自引率

20.50%

发文量

631

审稿时长

3.8 months

期刊介绍： The mission of the journal is to publish high quality work from experimental, theoretical, and computational investigations on the fundamentals of combustion phenomena and closely allied matters. While submissions in all pertinent areas are welcomed, past and recent focus of the journal has been on: Development and validation of reaction kinetics, reduction of reaction mechanisms and modeling of combustion systems, including: Conventional, alternative and surrogate fuels; Pollutants; Particulate and aerosol formation and abatement; Heterogeneous processes. Experimental, theoretical, and computational studies of laminar and turbulent combustion phenomena, including: Premixed and non-premixed flames; Ignition and extinction phenomena; Flame propagation; Flame structure; Instabilities and swirl; Flame spread; Multi-phase reactants. Advances in diagnostic and computational methods in combustion, including: Measurement and simulation of scalar and vector properties; Novel techniques; State-of-the art applications. Fundamental investigations of combustion technologies and systems, including: Internal combustion engines; Gas turbines; Small- and large-scale stationary combustion and power generation; Catalytic combustion; Combustion synthesis; Combustion under extreme conditions; New concepts.