Theoretical study of H-abstraction reactions of DMM by NH2/NO/NO2 and kinetic modeling on combustion of DMM/NH3 mixtures

IF 5.9 2区工程技术 Q2 ENERGY & FUELS

Combustion and Flame Pub Date : 2026-05-01 Epub Date: 2026-02-26 DOI:10.1016/j.combustflame.2026.114885

Mingwei Gong , Dan Liu , Lidong Zhang

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引用次数: 0

Abstract

The H-abstraction reactions of dimethoxymethane (DMM, CH₃OCH₂OCH₃) by amino (NH₂)/nitric oxide (NO)/nitrogen dioxide (NO₂) are investigated in this work to improve the combustion kinetic modeling of DMM/ammonia (NH₃) mixtures. The potential energy surfaces (PESs) for these reactions are obtained by employing the CCSD(T)/CBS//M06–2X/6–311G(d,p) method. The related rate constants are calculated based on conventional transition state theory (CTST) and rigid rotor harmonic oscillator (RRHO) assumptions within the temperature range of 300–2000 K. The role of DMM+NH₂/NO/NO₂ reactions in DMM/NH₃ combustion is quantified via laminar burning velocity (LBVs), ignition delay times (IDTs), and species concentration profiles simulations, revealing their impact on flame stabilization and ignition kinetics. The updated kinetic modeling accurately predicts experimental LBVs across DMM blending ratios of 20 %, 40 %, 60 %, and 100 %. Compared to the earlier kinetic modeling, the updated mechanism predicts shorter ignition delay times (IDTs) for DMM/NH₃ blends (5–50 % DMM) across 1–10 bar, equivalence ratio (ϕ) of 0.5, and 1193–1852 K, indicating enhanced treatment of key H-abstraction reactions (DMM+NH₂/NO/NO₂). Additionally, the model validation is extended to species evolution in flow reactors, further confirming the reliability of the kinetic scheme. This study establishes critical rate constants for DMM/NH₃ combustion kinetics while providing a foundational framework for investigating polyoxymethylene dimethyl ethers (PODE, also known as OME)/NH₃ mixture combustion.

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NH2/NO/NO2对DMM吸氢反应的理论研究及DMM/NH3混合物燃烧动力学模拟

研究了氨基(NH2)/一氧化氮(NO)/二氧化氮（NO2）对二甲氧基甲烷（DMM, CH3OCH2OCH3）的吸氢反应，以改进DMM/氨（NH3）混合物的燃烧动力学模型。利用CCSD(T)/CBS// M06-2X / 6-311G （d,p）方法得到了这些反应的势能面。在300-2000 K的温度范围内，基于传统的过渡态理论（CTST）和刚性转子谐振子（RRHO）假设计算了相关的速率常数。通过层流燃烧速度（LBVs）、点火延迟时间（IDTs）和物质浓度分布模拟，量化了DMM+NH2/NO/NO2反应在DMM/NH3燃烧中的作用，揭示了它们对火焰稳定性和点火动力学的影响。更新的动力学模型准确地预测了DMM混合比例为20%，40%，60%和100%的实验LBVs。与早期的动力学模型相比，更新的机制预测DMM/NH3混合物（5 - 50% DMM）在1-10 bar范围内的点火延迟时间（IDTs）更短，等效比（φ）为0.5,1193-1852 K，表明关键h提取反应（DMM+NH2/NO/NO2）的处理得到加强。此外，将模型验证扩展到流动反应器中的物种进化，进一步证实了动力学方案的可靠性。本研究建立了DMM/NH3燃烧动力学的临界速率常数，同时为研究聚氧二甲基醚（PODE，也称为OME）/NH3混合物燃烧提供了基础框架。

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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.