大分子直链烷烃O<sub>2</sub>QOOH异构化反应速率规则优化与验证

曹军; 张鑫; 洪聪结; 孙五川; 周雄; 康玉东; 康松; 邓远灏; 黄佐华; 张英佳

doi:10.7652/xjtuxb202205001

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大分子直链烷烃O₂QOOH异构化反应速率规则优化与验证

专题清洁燃烧 | 更新时间：2025-07-09

- 大分子直链烷烃O₂QOOH异构化反应速率规则优化与验证
- Optimization and Verification of Rate Rules for O₂QOOH Isomerization Reaction of Macromolecular Straight-Chain Alkane
- 西安交通大学学报 2022年56卷第5期页码：1-11
- 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：
  
  : 2021-11-26。作者简介: 曹军(1996—),男,硕士生
  张英佳(通信作者),男,教授,博士生导师。基金项目: 国家科技重大专项资助项目(J2019-III-0004-0047)
- 基金信息：
  
  : 2021-11-26。作者简介: 曹军(1996—),男,硕士生;张英佳(通信作者),男,教授,博士生导师。基金项目: 国家科技重大专项资助项目(J2019-III-0004-0047);中航发四川燃气涡轮研究院外委课题资助项目(KTZX-030120210007)
- DOI：10.7652/xjtuxb202205001
  中图分类号： TK49
- 网络首发：2022-05-10，
  
  纸质出版：2022
- 稿件说明：
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曹军, 张鑫, 洪聪结, 等. 大分子直链烷烃O₂QOOH异构化反应速率规则优化与验证[J]. 西安交通大学学报, 2022,56(5):1-11. DOI: 10.7652/xjtuxb202205001.

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.
曹军, 张鑫, 洪聪结, 等. 大分子直链烷烃O₂QOOH异构化反应速率规则优化与验证[J]. 西安交通大学学报, 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

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大分子直链烷烃O2QOOH异构化反应速率规则优化与验证

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

大分子直链烷烃O₂QOOH异构化反应速率规则优化与验证

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