Optimization and Verification of Rate Rules for O<sub>2</sub>QOOH Isomerization Reaction of Macromolecular Straight-Chain Alkane

CAO Jun; ZHANG Xin; HONG Congjie; SUN Wuchuan; ZHOU Xiong; KANG Yudong; KANG Song; DENG Yuanhao; HUANG Zuohua; ZHANG Yingjia

doi:10.7652/xjtuxb202205001

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Optimization and Verification of Rate Rules for O₂QOOH Isomerization Reaction of Macromolecular Straight-Chain Alkane

更新时间：2025-07-09

- Optimization and Verification of Rate Rules for O₂QOOH Isomerization Reaction of Macromolecular Straight-Chain Alkane
- Vol. 56, Issue 5, Pages: 1-11(2022)
- 作者机构：
  
  1. 西安交通大学动力工程多相流国家重点实验室,西安,710049
  2. 中国航空发动机集团有限公司四川燃气涡轮研究院,成都,610500
- 作者简介：
- 基金信息：
- DOI：10.7652/xjtuxb202205001
  CLC： TK49
- Online First：10 May 2022，
  
  Published：2022
- 稿件说明：
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CAO Jun, ZHANG Xin, HONG Congjie, et al. Optimization and Verification of Rate Rules for O₂QOOH Isomerization Reaction of Macromolecular Straight-Chain Alkane[J]. 2022, 56(5): 1-11. DOI: 10.7652/xjtuxb202205001.
DOI：

CAO Jun, ZHANG Xin, HONG Congjie, et al. Optimization and Verification of Rate Rules for O₂QOOH Isomerization Reaction of Macromolecular Straight-Chain Alkane[J]. 2022, 56(5): 1-11. DOI: 10.7652/xjtuxb202205001. DOI：

摘要

为了探究大分子直链烷烃模型低温反应类速率规则的有效性

对现有模型及O

QOOH异构化重要反应类进行了速率规则优化和实验验证。本文以正癸烷为研究对象

利用激波管反射激波方法测量了不同温度(650～1 550 K)、不同压力(0.1 MPa、0.5 MPa、2.0 MPa)、两种当量比(0.5和1.0)条件下的点火延迟期; 结合统计学方法推导出该反应类的理论计算值

并对其构建了新速率规则。实验结果表明

0.1 MPa工况下

由于反应竞争加剧

目标燃料两个当量比的点火延迟期存在交叉点; 0.5 MPa和2.0 MPa下

正癸烷点火延迟时间均出现负温度系数(NTC)行为。对比发现

劳伦斯利弗莫尔国家实验室(LLNL)模型和蔡黎明(CAI)模型预测偏差主要集中在NTC区域

LLNL模型预测值与实验值最大偏差达11 059 μs。速率分析表明

在O

QOOH异构化反应类1

4-H、1

5-H以及1

7-H氢原子迁移过程中

LLNL模型使用的速率系数与速率规则限值最大差异达3.5个数量级

说明直接类比RO

异构化方法获得目标异构化反应速率存在较大偏差。耦合更新速率规则后

LLNL优化模型在660～1 050 K温度区间内对点火延迟期预测变快; CAI优化模型在800 K温度以下的预测略微加快

高压下模型预测值与实验值吻合较好。该研究发展的速率规则可为大分子直链烷烃低温O

QOOH异构化过程的动力学描述提供新的参考。

Abstract

To explore the reliability of existing rate rule of reaction class for describing low temperature kinetics of macromolecular straight-chain alkanes

two widely used chemical kinetic models

LLNL and CAI models

were tested experimentally

and a rate rule of selected important reaction class of O

QOOH isomerization was verified theoretically. In this study

ignition delay times of n-decane were measured in reflected shock conditions covering temperature range of 650-1 550 K

pressures of 0.1

0.5 and 2.0 MPa

and equivalence ratios of 0.5 and 1.0. Theoretical calculation values and new rate rule of the target reaction class were initially derived by combining with statistical methods. Experimental results revealed that the ignition delay times of n-decane exhibit crossover behavior due to increased reaction competition at both equivalence ratios at high temperatures and 0.1 MPa

while present NTC behavior at 0.5 and 2.0 MPa. Both LLNL and CAI models showed generally poor predictions in the ignition delay times especially in NTC regime

and LLNL model even showed a deviation from the experimental data up to 11 059 μs. It is found that the maximum difference of rate coefficient applied in LLNL model and the lower limit of the rate rule can be nearly 3.5 orders of magnitude for the migration process of O

QOOH isomerization reactions involving 1

4-H

5-H and 1

7-H H-atom transition. It implies that the rate coefficients for O

QOOH isomerization adopting directly analogy with RO

isomerization could remain unacceptable uncertainty. After the updated rate rule is incorporated

the LLNL model shows a faster prediction in the ignition delay time over temperature range of 660-1 050 K

while the CAI model shows a slightly faster prediction below 800 K and agrees well with the experimental measurements under high pressure. The new rate rule can provide a reference for the kinetic description in low temperature O

QOOH isomerization mechanism of macromolecular straight-chain alkanes.

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references

VASU S S, DAVIDSON D F, HANSON R K. Jet fuel ignition delay times: shock tube experiments over wide conditions and surrogate model predictions [J]. Combustion and Flame, 2008, 152(1/2): 125-143.

许星长, 伍宏环, 黄文林, 等. 正庚烷氧化基态OH基浓度时程吸收光谱诊断 [J]. 西安交通大学学报, 2021, 55(9): 113-120.

XU Xingchang, WU Honghuan, HUANG Wenlin, et al. Laser absorption spectrum measurement of OH concentration time-histories in n-heptane oxidation [J]. Journal of Xi'an Jiaotong University, 2021, 55(9): 113-120.

张英佳, 黄佐华, 王金华, 等. 激波管研究煤油/空气混合气的自着火特性 [J]. 科学通报, 2011, 56(1): 85-93.

ZHANG Yingjia, HUANG Zuohua, WANG Jinhua, et al. Self ignition characteristics of kerosene/air mixture in shock tube [J]. Chinese Science Bulletin, 2011, 56(1): 85-93.

徐佳琪, 郭俊江, 刘爱科, 等. RP-3替代燃料自点火燃烧机理构建及动力学模拟 [J]. 物理化学学报, 2015, 31(4): 643-652.

XU Jiaqi, GUO Junjiang, LIU Aike, et al. Construction of autoignition mechanisms for the combustion of RP-3 surrogate fuel and kinetics simulation [J]. Acta Physico-Chimica Sinica, 2015, 31(4): 643-652.

李军, 邵菊香, 刘存喜, 等. 碳氢燃料热裂解机理及化学动力学模拟 [J]. 化学学报, 2010, 68(3): 239-245.

LI Jun, SHAO Juxiang, LIU Cunxi, et al. Pyrolysis mechanism of hydrocarbon fuels and kinetic modeling [J]. Acta Chimica Sinica, 2010, 68(3): 239-245.

齐飞, 李玉阳, 张晓愿. 燃烧反应动力学研究进展与展望 [J]. 中国科学基金, 2015, 29(3): 187-195.

QI Fei, LI Yuyang, ZHANG Xiaoyuan. Recent advances and perspectives of combustion kinetic [J]. Bulletin of National Natural Science Foundation of China, 2015, 29(3): 187-195.

刘靖, 胡二江, 黄佐华, 等. RP-3航空煤油模拟替代燃料的着火延迟特性 [J]. 推进技术, 2021, 42(2): 467-473.

LIU Jing, HU Erjiang, HUANG Zuohua, et al. Ignition delay characteristics of a surrogate fuel for RP-3 kerosene [J]. Journal of Propulsion Technology, 2021, 42(2): 467-473.

SUN Wuchuan, HUANG Wenlin, QIN Xiaokang, et al. Water impact on the auto-ignition of kerosene/air mixtures under combustor relevant conditions [J]. Fuel, 2020, 267: 117184.

EITENEER B, FRENKLACH M. Experimental and modeling study of shock-tube oxidation of acetylene [J]. International Journal of Chemical Kinetics, 2003, 35(9): 391-414.

HIDAKA Y, HENMI Y, OHONISHI T et al. Shock-tube and modeling study of diacetylene pyrolysis and oxidation [J]. Combustion and Flame, 2002, 130(1/2): 62-82.

BAULCH D L, COBOS C J, COX R A, et al. Evaluated kinetic data for combustion modelling [J]. Journal of Physical and Chemical Reference Data, 1992, 21(3): 411-734.

LU Tianfeng, LAW C K. Toward accommodating realistic fuel chemistry in large-scale computations [J]. Progress in Energy and Combustion Science, 2009, 35(2): 192-215.

SARATHY S M, WESTBROOK C K, MEHL M, et al. Comprehensive chemical kinetic modeling of the oxidation of 2-methylalkanes from C7 to C20 [J]. Combustion and Flame, 2011, 158(12): 2338-2357.

PRAGER J, NAJM H N, SARGSYAN K, et al. Uncertainty quantification of reaction mechanisms accounting for correlations introduced by rate rules and fitted Arrhenius parameters [J]. Combustion and Flame, 2013, 160(9): 1583-1593.

梁兴雨, 刘志伟, 王昆, 等. 4类碳氢燃料的高温燃烧反应简化建模 [J]. 西安交通大学学报, 2021, 55(2): 27-37.

LIANG Xingyu, LIU Zhiwei, WANG Kun, et al. Simplified kinetic modeling of high temperature combustion reactions of four hydrocarbon fuels [J]. Journal of Xi'an Jiaotong University, 2021, 55(2): 27-37.

RANZI E, GAFFURI P, FARAVELLI T, et al. A wide-range modeling study of n-heptane oxidation [J]. Combustion and Flame, 1995, 103(1/2): 91-106.

CURRAN H J, GAFFURI P, PITZ W J, et al. A comprehensive modeling study of n-heptane oxidation [J]. Combustion and Flame, 1998, 114(1/2): 149-177.

BUGLER J, SOMERS K P, SILKE E J, et al. Revisiting the kinetics and thermodynamics of the low-temperature oxidation pathways of alkanes: a case study of the three pentane isomers [J]. The Journal of Physical Chemistry: A, 2015, 119(28): 7510-7527.

CAI Liming, PITSCH H. Mechanism optimization based on reaction rate rules [J]. Combustion and Flame, 2014, 161(2): 405-415.

ZHANG Kuiwen, BANYON C, TOGBÉ C, et al. An experimental and kinetic modeling study of n-hexane oxidation [J]. Combustion and Flame, 2015, 162(11): 4194-4207.

WANG Zhandong, SARATHY S M. Third O2 addition reactions promote the low-temperature auto-ignition of n-alkanes [J]. Combustion and Flame, 2016, 165: 364-372.

CAI Liming, PITSCH H, MOHAMED S Y, et al. Optimized reaction mechanism rate rules for ignition of normal alkanes [J]. Combustion and Flame, 2016, 173: 468-482.

ZHANG Kuiwen, BANYON C, BURKE U, et al. An experimental and kinetic modeling study of the oxidation of hexane isomers: developing consistent reaction rate rules for alkanes [J]. Combustion and Flame, 2019, 206: 123-137.

SHARMA S, RAMAN S, GREEN W H. Intramolecular Hydrogen migration in alkylperoxy and hydroperoxyalkylperoxy radicals: accurate treatment of hindered rotors [J]. The Journal of Physical Chemistry: A, 2010, 114(18): 5689-5701.

MIYOSHI A. Systematic computational study on the unimolecular reactions of alkylperoxy(RO2), hydroperoxyalkyl(QOOH), and hydroperoxyalkylperoxy(O2QOOH)radicals [J]. The Journal of Physical Chemistry: A, 2011, 115(15): 3301-3325.

MOHAMED S Y, DAVIS A C, AL RASHIDI M J, et al. High-Pressure limit rate rules for α-H isomerization of hydroperoxyalkylperoxy radicals [J]. The Journal of Physical Chemistry: A, 2018, 122(14): 3626-3639.

潘伦, 张英佳, 黄佐华. C2H6/H2混合气着火特性的实验与化学动力学研究 [J]. 西安交通大学学报, 2014, 48(9): 49-54.

PAN Lun, ZHANG Yingjia, HUANG Zuohua. Experimental and kinetic research on ignition characteristics of C2H6/H2 mixtures [J]. Journal of Xi'an Jiaotong University, 2014, 48(9): 49-54.

张英佳, 孙五川, 邓福泉, 等. N2O对乙烯自点火敏化作用的实验和理论研究 [J]. 西安交通大学学报, 2019, 53(1): 86-92.

ZHANG Yingjia, SUN Wuchuan, DENG Fuquan, et al. Experimental and theoretical study on the sensitization of N2O to ethylene auto-ignition [J]. Journal of Xi'an Jiaotong University, 2019, 53(1): 86-92.

PETERSEN E L, RICKARD M J A, CROFTON M W, et al. A facility for gas-and condensed-phase measurements behind shock waves [J]. Measurement Science and Technology, 2005, 16(9): 1716-1729.

DIEGO C P R D. CHEMKIN-PRO 15112, Reaction Design: San Diego [CP/OL]. [2011-12-01]. http:∥www.reactiondesign.com/products/chemkin.

张云华. 统计学中四分位数的计算 [J]. 中国高新技术企业, 2009(20): 173-174.

ZHANG Yunhua. Calculation of quartile in statistics [J]. China High-Tech Enterprises, 2009(20): 173-174.

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⁰

Optimization and Verification of Rate Rules for O2QOOH Isomerization Reaction of Macromolecular Straight-Chain Alkane

DOI：10.7652/xjtuxb202205001

摘要

Abstract

关键词

Keywords

references

Optimization and Verification of Rate Rules for O₂QOOH Isomerization Reaction of Macromolecular Straight-Chain Alkane