大分子直链烷烃O_(2)QOOH异构化反应速率规则优化与验证  

Optimization and Verification of Rate Rules for O_(2)QOOH Isomerization Reaction of Macromolecular Straight-Chain Alkane

作　　者：曹军[1] 张鑫[1] 洪聪结 孙五川 周雄 康玉东 康松 邓远灏 黄佐华[1] 张英佳[1] CAO Jun;ZHANG Xin;HONG Congjie;SUN Wuchuan;ZHOU Xiong;KANG Yudong;KANG Song;DENG Yuanhao;HUANG Zuohua;ZHANG Yingjia(State Key Laboratory of Multiphase Flows in Power Engineering, Xi’an Jiaotong University, Xi’an 710049, China;Sichuan Gas Turbine Establishment of AECC, Chengdu 610500, China)

机构地区：[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

出　　处：《西安交通大学学报》2022年第5期1-11,共11页Journal of Xi'an Jiaotong University

基　　金：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)。

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_(2)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(650~1550 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11059μs。速率分析表明,在O_(2)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_(2)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660~1050 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_(2)QOOH异构化过程的动力学描述提供新的参考。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_(2)QOOH isomerization was verified theoretically.In this study,ignition delay times of n-decane were measured in reflected shock conditions covering temperature range of 650-1550 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 11059μs.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_(2)QOOH isomerization reactions involving 1,4-H,1,5-H and 1,7-H H-atom transition.It implies that the rate coefficients for O_(2)QOOH isomerization adopting directly analogy with RO_(2) 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 660-1050 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_(2)QOOH isomerization mechanism of macromolecular straight-chain alkanes.

关 键 词：正癸烷 点火延迟期 激波管 O_(2)QOOH异构化 速率规则 

分 类 号：TK49[动力工程及工程热物理—动力机械及工程]