Investigation of Di-tert-butyl peroxide combustion: time-resolved speciation, laminar flame speed, and model evaluation

IF 5.8 2区工程技术 Q2 ENERGY & FUELS

Combustion and Flame Pub Date : 2025-07-24 DOI:10.1016/j.combustflame.2025.114350

Congjie Hong , Jiabiao Zou , Janardhanraj Subburaj , Ayman M. Elbaz , William L. Roberts , Yingjia Zhang , Zuohua Huang , Aamir Farooq

{"title":"Investigation of Di-tert-butyl peroxide combustion: time-resolved speciation, laminar flame speed, and model evaluation","authors":"Congjie Hong , Jiabiao Zou , Janardhanraj Subburaj , Ayman M. Elbaz , William L. Roberts , Yingjia Zhang , Zuohua Huang , Aamir Farooq","doi":"10.1016/j.combustflame.2025.114350","DOIUrl":null,"url":null,"abstract":"<div><div>Di‑tert‑butyl peroxide (DTBP), a cetane improver, consists of two tert‑butoxy groups bonded by a weak peroxide bond. A thorough understanding of the combustion mechanisms of DTBP is essential for its effective use as a fuel additive. This study systematically investigates the pyrolysis and oxidation characteristics of DTBP through a combination of experimental measurements and kinetic modeling. Laser absorption spectroscopy was employed to achieve time-resolved quantification of key species, including CO, CO<sub>2</sub>, OH, and H<sub>2</sub>O, during DTBP pyrolysis and oxidation under conditions spanning 1265 - 2000 K and 1.1 - 1.6 bar. The laminar flame speed of DTBP was measured for the first time over a range of equivalence ratios (0.65 - 1.4), initial pressures (0.5 - 2 bar), and a fixed initial temperature of 373 ± 3 K. These experimental results provide essential constraints for optimizing and validating the DTBP kinetic model. The proposed model significantly improved the accuracy of predictions for ignition delay times and laminar flame speeds. Furthermore, the model demonstrated excellent performance in capturing the second-stage ignition delay, overcoming the limitations of previous models. However, the current model still exhibits noticeable deviations in predictions below 1300 K, particularly in the formation dynamics of key species such as CO. To improve the model’s accuracy under these conditions, further high-fidelity quantum chemical calculations are needed to refine the rate constants of additional unimolecular decomposition and hydrogen abstraction pathways of DTBP. Overall, by incorporating the latest sub-mechanism of acetone oxidation and updated rate constants for DTBP decomposition reactions, this study provides valuable experimental data and kinetic insights to advance combustion kinetic models for oxygenated fuels and support the development of high-efficiency combustion technologies.</div></div>","PeriodicalId":280,"journal":{"name":"Combustion and Flame","volume":"280 ","pages":"Article 114350"},"PeriodicalIF":5.8000,"publicationDate":"2025-07-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Combustion and Flame","FirstCategoryId":"5","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0010218025003876","RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"ENERGY & FUELS","Score":null,"Total":0}

引用次数: 0

Abstract

Di‑tert‑butyl peroxide (DTBP), a cetane improver, consists of two tert‑butoxy groups bonded by a weak peroxide bond. A thorough understanding of the combustion mechanisms of DTBP is essential for its effective use as a fuel additive. This study systematically investigates the pyrolysis and oxidation characteristics of DTBP through a combination of experimental measurements and kinetic modeling. Laser absorption spectroscopy was employed to achieve time-resolved quantification of key species, including CO, CO₂, OH, and H₂O, during DTBP pyrolysis and oxidation under conditions spanning 1265 - 2000 K and 1.1 - 1.6 bar. The laminar flame speed of DTBP was measured for the first time over a range of equivalence ratios (0.65 - 1.4), initial pressures (0.5 - 2 bar), and a fixed initial temperature of 373 ± 3 K. These experimental results provide essential constraints for optimizing and validating the DTBP kinetic model. The proposed model significantly improved the accuracy of predictions for ignition delay times and laminar flame speeds. Furthermore, the model demonstrated excellent performance in capturing the second-stage ignition delay, overcoming the limitations of previous models. However, the current model still exhibits noticeable deviations in predictions below 1300 K, particularly in the formation dynamics of key species such as CO. To improve the model’s accuracy under these conditions, further high-fidelity quantum chemical calculations are needed to refine the rate constants of additional unimolecular decomposition and hydrogen abstraction pathways of DTBP. Overall, by incorporating the latest sub-mechanism of acetone oxidation and updated rate constants for DTBP decomposition reactions, this study provides valuable experimental data and kinetic insights to advance combustion kinetic models for oxygenated fuels and support the development of high-efficiency combustion technologies.

查看原文本刊更多论文

过氧化二叔丁基燃烧的研究：时间分辨形态、层流火焰速度和模型评价

过氧化二叔丁基（DTBP）是一种十六烷改进剂，由两个叔丁基通过弱过氧化物键连接而成。全面了解DTBP的燃烧机理是其作为燃料添加剂有效使用的必要条件。本研究通过实验测量和动力学建模相结合的方法，系统地研究了DTBP的热解和氧化特性。采用激光吸收光谱技术，在1265 ~ 2000 K和1.1 ~ 1.6 bar条件下，对DTBP热解和氧化过程中CO、CO2、OH和H2O等关键物质进行了时间分辨定量。在等效比（0.65 ~ 1.4）、初始压力（0.5 ~ 2 bar）和固定初始温度（373±3k）范围内，首次测量了DTBP的层流火焰速度。这些实验结果为优化和验证DTBP动力学模型提供了必要的约束条件。该模型显著提高了点火延迟时间和层流火焰速度的预测精度。此外，该模型克服了以往模型的局限性，在捕捉第二级点火延迟方面表现出优异的性能。然而，目前的模型在1300 K以下的预测中仍然表现出明显的偏差，特别是在CO等关键物种的形成动力学中。为了提高模型在这些条件下的准确性，需要进一步的高保真量子化学计算来完善DTBP的其他单分子分解和氢提取途径的速率常数。综上所述，本研究结合了最新的丙酮氧化子机制和最新的DTBP分解反应速率常数，为完善含氧燃料的燃烧动力学模型和支持高效燃烧技术的发展提供了有价值的实验数据和动力学见解。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

求助全文

约1分钟内获得全文求助全文

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.