Abstract
Di-isobutylene has received significant attention as a promising fuel blendstock, as it can be synthesized via biological routes and is a short-listed molecule from the Co-Optima initiative. Di-isobutylene is also popularly used as an alkene representative in multi-component surrogate models for engine studies of gasoline fuels. However, there is limited experimental data available in the literature for neat di-isobutylene under engine-like conditions. Hence, most existing di-isobutylene models have not been extensively validated, particularly at lower temperatures (< 1000 K). Most gasoline surrogate models include the di-isobutylene sub-mechanism published by Metcalfe et al. [1] with little or no modification. The current study is undertaken to develop a detailed kinetic model for di-isobutylene and validate the model using a wide range of relevant experimental data. Part 1 of this study exclusively focuses on the low- to intermediate temperature kinetics of di-isobutylene. An upcoming part 2 discusses the high-temperature model development and validation of the relevant experimental targets. Ignition delay time measurements for the di-isobutylene isomers were performed at pressures ranging from 15 – 30 bar at equivalence ratios of 0.5, 1.0, and 2.0 diluted in air and in the temperature range 650 – 900 K using two independent rapid compression machine facilities. In addition, measurements of species identified during the oxidation of these isomers were performed in a jet-stirred reactor and in a rapid compression machine. A detailed kinetic model for the di-isobutylene isomers is developed to capture the wide range of new experimental targets. For the first time, a comprehensive low-temperature chemistry submodel is included. The differences in the important reaction pathways for the accurate prediction of the oxidation of the two DIB isomers are compared using reaction path analysis. The most sensitive reactions controlling the ignition delay times of the DIB isomers under the pressure and temperature conditions necessary for autoignition in engines are identified.
| Original language | English |
|---|---|
| Article number | 112301 |
| Journal | Combustion and Flame |
| Volume | 251 |
| DOIs | |
| State | Published - May 2023 |
Funding
The authors at NUI Galway recognize funding support from Science Foundation Ireland (SFI) via project numbers 15/IA/3177 and 16/SP/3829. The work at LLNL was performed under the auspices of the U.S. Department of Energy (DOE) by Lawrence Livermore National Laboratory under Contract DE-AC52–07NA27344 and was conducted as part of the Co-Optimization of Fuels & Engines (Co-Optima) initiative sponsored by the DOE Office of Energy Efficiency and Renewable Energy (EERE), Bioenergy Technologies and Vehicle Technologies Offices. Work at the National Renewable Energy Laboratory was performed under Contract No. DE347AC36-99GO10337 as part of the Co-Optimization of Fuels & Engines (Co-Optima) initiative sponsored by the DOE Office of Energy Efficiency and Renewable Energy (EERE), Bioenergy Technologies and Vehicle Technologies Offices. This research performed in ULille was funded by TotalEnergies OneTech and is a contribution to the CPER research project Climibio. HS and GV thank the Région Hauts-de-France, and the Ministère de l'Enseignement Supérieur et de la Recherche (CPER Climibio), and the European Fund for Regional Economic Development for their financial support. CNRS Orléans received support from the CAPRYSSES project (ANR- 11-LABX-006–01) funded by the PIA (Programme d'Investissement d'Avenir). The study was supported by the grant from the Russian Science Foundation (project No. 19-79-00325). The authors would also like to acknowledge the financial support from the Energy Agency via the Centre for Combustion Science and Technology [Project KC-CECOST 22538-4], Sweden. M.S., A.B, and P.H acknowledge funding by the Swiss Federal Office of Energy (SI/501269-01). The pyrolysis measurements (presented in Part II) were carried out at the VUV (x04db) beamline of the Swiss Light Source storage ring, located at Paul Scherrer Institute in Villigen (Switzerland). This report was prepared as an account of work sponsored by an agency of the United States Government. Neither the United States Government nor any agency thereof, nor any of their employees, makes any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Government or any agency thereof. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Government or any agency thereof. The authors at NUI Galway recognize funding support from Science Foundation Ireland (SFI) via project numbers 15/IA/3177 and 16/SP/3829. The work at LLNL was performed under the auspices of the U.S. Department of Energy (DOE) by Lawrence Livermore National Laboratory under Contract DE-AC52–07NA27344 and was conducted as part of the Co-Optimization of Fuels & Engines (Co-Optima) initiative sponsored by the DOE Office of Energy Efficiency and Renewable Energy (EERE), Bioenergy Technologies and Vehicle Technologies Offices. Work at the National Renewable Energy Laboratory was performed under Contract No. DE347AC36-99GO10337 as part of the Co-Optimization of Fuels & Engines (Co-Optima) initiative sponsored by the DOE Office of Energy Efficiency and Renewable Energy (EERE), Bioenergy Technologies and Vehicle Technologies Offices. This research performed in ULille was funded by TotalEnergies OneTech and is a contribution to the CPER research project Climibio. HS and GV thank the Région Hauts-de-France, and the Ministère de l'Enseignement Supérieur et de la Recherche (CPER Climibio), and the European Fund for Regional Economic Development for their financial support. CNRS Orléans received support from the CAPRYSSES project (ANR- 11-LABX-006–01) funded by the PIA (Programme d'Investissement d'Avenir). The study was supported by the grant from the Russian Science Foundation (project No. 19-79-00325). The authors would also like to acknowledge the financial support from the Energy Agency via the Centre for Combustion Science and Technology [Project KC-CECOST 22538-4], Sweden. M.S. A.B, and P.H acknowledge funding by the Swiss Federal Office of Energy (SI/501269-01). The pyrolysis measurements (presented in Part II) were carried out at the VUV (x04db) beamline of the Swiss Light Source storage ring, located at Paul Scherrer Institute in Villigen (Switzerland).
Keywords
- Chemical kinetics
- Di-isobutylene
- Jet-stirred reactor
- Kinetic modeling
- Rapid compression machine