An experimental and chemical kinetic modeling study of 1,3-butadiene combustion: Ignition delay time and laminar flame speed measurements

• Published in: Combustion and flame Vol. 197; pp. 423 - 438
• Main Authors: Zhou, Chong-Wen, Li, Yang, Burke, Ultan, Banyon, Colin, Somers, Kieran P., Ding, Shuiting, Khan, Saadat, Hargis, Joshua W., Sikes, Travis, Mathieu, Olivier, Petersen, Eric L., AlAbbad, Mohammed, Farooq, Aamir, Pan, Youshun, Zhang, Yingjia, Huang, Zuohua, Lopez, Joseph, Loparo, Zachary, Vasu, Subith S., Curran, Henry J.
• Format: Journal Article
• Language: English
• Published: New York Elsevier Inc 01-11-2018; Elsevier BV
• Subjects: 1,3-butadiene oxidation; Ab initio calculations; Adducts; Allene; Atmospheric models; Bonds; Butadiene; Chemical kinetic modeling; Combustion chambers; Compression tests; Computer simulation; Delay; Delay time; Equivalence ratio; Flame speed; Flames; Ignition; Organic chemistry; Oxidation; Radicals; Rapid compression machine; Rate constants; Reaction kinetics; Reactivity; Sensitivity analysis; Shock tube; Shock tubes; Simulation; Thermochemistry; Thermodynamics; Vinyl radical; Shock tube; Rapid compression machine; Ab initio calculations; 1,3-butadiene oxidation; Flame speed; Chemical kinetic modeling
• ISSN: 0010-2180; 1556-2921
• DOI: 10.1016/j.combustflame.2018.08.006

Ignition delay times for 1,3-butadiene oxidation were measured in five different shock tubes and in a rapid compression machine (RCM) at thermodynamic conditions relevant to practical combustors. The ignition delay times were measured at equivalence ratios of 0.5, 1.0, and 2.0 in ‘air’ at pressures of 10, 20 and 40 atm in both the shock tubes and in the RCM. Additional measurements were made at equivalence ratios of 0.3, 0.5, 1.0 and 2.0 in argon, at pressures of 1, 2 and 4 atm in a number of different shock tubes. Laminar flame speeds were measured at unburnt temperatures of 295 K, 359 K and 399 K at atmospheric pressure in the equivalence ratio range of 0.6–1.7, and at a pressure of 5 atm at equivalence ratios in the range 0.6–1.4. These experimental data were then used as validation targets for a newly developed detailed chemical kinetic mechanism for 1,3-butadiene oxidation.
A detailed chemical kinetic mechanism (AramcoMech 3.0) has been developed to describe the combustion of 1,3-butadiene and is validated by a comparison of simulation results to the new experimental measurements. Important reaction classes highlighted via sensitivity analyses at different temperatures include: (a) ȮH radical addition to the double bonds on 1,3-butadiene and their subsequent reactions. The branching ratio for addition to the terminal and central double bonds is important in determining the reactivity at low-temperatures. The alcohol-alkene radical adducts that are subsequently formed can either react with HȮ2 radicals in the case of the resonantly stabilized radicals or O2 for other radicals. (b) HȮ2 radical addition to the double bonds in 1,3-butadiene and their subsequent reactions. This reaction class is very important in determining the fuel reactivity at low and intermediate temperatures (600–900 K). Four possible addition reactions have been considered. (c) 3Ö atom addition to the double bonds in 1,3-butadiene is very important in determining fuel reactivity at intermediate to high temperatures (> 800 K). In this reaction class, the formation of two stable molecules, namely CH2O + allene, inhibits reactivity whereas the formation of two radicals, namely Ċ2H3 and ĊH2CHO, promotes reactivity. (d) Ḣ atom addition to the double bonds in 1,3-butadiene is very important in the prediction of laminar flame speeds. The formation of ethylene and a vinyl radical promotes reactivity and it is competitive with H-atom abstraction by Ḣ atoms from 1,3-butadiene to form the resonantly stabilized Ċ4H5-i radical and H2 which inhibits reactivity. Ab initio chemical kinetics calculations were carried out to determine the thermochemistry properties and rate constants for some of the important species and reactions involved in the model development. The present model is a decent first model that captures most of the high-temperature IDTs and flame speeds quite well, but there is room for considerable improvement especially for the lower temperature chemistry before a robust model is developed.