A DFT study of oxidation reaction for ethanol molecule and representative conventional molecule in gasoline was performed. At first, the homolytic dissociation energy of the different C-H bond in ethanol and hydrocarbon molecules was calculated and the C-H active sites most likely to be attacked by oxygen molecule were obtained. Then, the reaction barrier of oxidation initiation reaction for different molecules was compared to conclude that the barrier energy of ethanol molecule was lower than the conventional gasoline molecule. It was found that the lower energy gap between the HOMO orbital of ethanol molecule and the LUMO orbital of oxygen molecule was the driving force to the oxidation initiation reaction. In addition, the possible further reaction paths of ethanol free radical after dehydrogenation have also been investigated, which may generate acetaldehyde or acetic acid. The two reaction paths actually existed at the same time, though compared with the acetic acid steps, the reaction path was shorter for generating acetaldehyde. It was indicated that ethanol gasoline is more prone to oxidation than conventional gasoline, which leads to changes in its molecular composition and physical and chemical properties. We should pay attention to the oxidation stability of ethanol gasoline during its storage and use.
| Published in | Journal of Energy and Natural Resources (Volume 9, Issue 1) |
| DOI | 10.11648/j.jenr.20200901.17 |
| Page(s) | 39-43 |
| Creative Commons |
This is an Open Access article, distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution and reproduction in any medium or format, provided the original work is properly cited. |
| Copyright |
Copyright © The Author(s), 2020. Published by Science Publishing Group |
Ethanol Gasoline, Oxidation Chain Radical Reaction, Molecular Simulation, DFT Method
| [1] | Nagpal JM, Joshi GC, Singh J, Kumar K. Studies on the nature of gum formed in cracked naphtas [J]. Oxid Commun 1998, 21 (4): 468-477. |
| [2] | Xue Dong, Yachao Chang, Bo Niu, et al. Development of a practical reaction model of polycyclic aromatic hydrocarbon (PAH) formation and oxidation for diesel surrogate fuel [J]. Fuel, 2020, 267: 117159. |
| [3] | Kinoshita M, Saito A, Matsushita S, Shibata H, Niwa Y. Study of deposit formation mechanism on gasoline injection nozzle [C]. SAE paper 1998, 19: 355-357. |
| [4] | Li Na, Long Jun, Zhao Yi, et al. Molecular Simulation of the Mechanism of Oxidation Gum Formation of Typical Gasoline Hydrocarbon [J]. Acta Petrolei Sinica (Petroleum Processing Section), 2018, 34 (2): 354-364. |
| [5] | Li Na, Long Jun, Zhao Yi, Tao Zhiping, Dai Zhenyu. DFT study of oxidation initiation for different compound in gasoline [J]. Journal of Clean Energy Technologies, 2017, 6 (3): 242-245. |
| [6] | Paul Lacey, Sandro Gail, Jean Marc Kientz, et al. Internal Fuel Injector Deposits [C]. SAE Paper 2011-01-1925. |
| [7] | Akio Tanaka, Koichi Yamada, Toshihiko Omori, et al. Inner Diesel Injector Deposit Formation Mechanism [C]. SAE Paper, 2013-01-2661. |
| [8] | Ji Xiang, Song Yingjin, Liu Rui, et al. Effect of oxidation decay of alcohol fuel engine on exhaust emission [J]. Journal of Harbin University of Commerce (Natural Sciences Edition), 2018, 34 (5): 573-576. |
| [9] | Nicholas J. Kuprowicz, Steven Zabarnick, Zachary J. West, et al. Use of Measured Species Class Concentrations with Chemical Kinetic Modeling for the Prediction of Autoxidation and Deposition of Jet Fuels [J]. Energy & Fuels 2007, 21, 530-544. |
| [10] | Ruben Epping, Stefanie Kerkering, Jan T. Andersson. Influence of Different Compound Classes on the Formation of Sediments in Fossil Fuels During Aging [J]. energy& fuels, 2014, 28: 5649-5656. |
| [11] | Zheng Guiling. Influence of compounds containing nitrogen, sulfur and oxygen on the oxidation stability of oil [D]. Beijing, China University of Petroleum, 2018. |
| [12] | Delley B. From molecules to solids with the Dmol3 approach [J]. J Chem Phys, 2000, 113 (18): 7756-7764. |
| [13] | Kohn W, Sham L J. Self-consistent equations including exchange and correlation effects [J]. Phys Rev, 1965, 140 (4A): A1133-A1138. |
| [14] | J. P. Perdew, K. Burke, M. Ernzerhof, Generalized gradient approximation made simple, Phys. Rev. Lett. 1996, 77: 3865-3868. |
| [15] | Kamlesh Kumar, Prashant Kumar, Penny Joshi, et al. IBX-TfOH mediated oxidation of alcohols to aldehydes and ketones under mild reaction conditions [J]. Tetrahedron Letters, 2020, 2: 151749. |
APA Style
Li Na, Han Lu, Guo Xin, Tao Zhiping, Long Jun. (2020). DFT Study of Oxidation Reaction Paths for Ethanol Gasoline. Journal of Energy and Natural Resources, 9(1), 39-43. https://doi.org/10.11648/j.jenr.20200901.17
ACS Style
Li Na; Han Lu; Guo Xin; Tao Zhiping; Long Jun. DFT Study of Oxidation Reaction Paths for Ethanol Gasoline. J. Energy Nat. Resour. 2020, 9(1), 39-43. doi: 10.11648/j.jenr.20200901.17
AMA Style
Li Na, Han Lu, Guo Xin, Tao Zhiping, Long Jun. DFT Study of Oxidation Reaction Paths for Ethanol Gasoline. J Energy Nat Resour. 2020;9(1):39-43. doi: 10.11648/j.jenr.20200901.17
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Download@article{10.11648/j.jenr.20200901.17,
author = {Li Na and Han Lu and Guo Xin and Tao Zhiping and Long Jun},
title = {DFT Study of Oxidation Reaction Paths for Ethanol Gasoline},
journal = {Journal of Energy and Natural Resources},
volume = {9},
number = {1},
pages = {39-43},
doi = {10.11648/j.jenr.20200901.17},
url = {https://doi.org/10.11648/j.jenr.20200901.17},
eprint = {https://article.sciencepublishinggroup.com/pdf/10.11648.j.jenr.20200901.17},
abstract = {A DFT study of oxidation reaction for ethanol molecule and representative conventional molecule in gasoline was performed. At first, the homolytic dissociation energy of the different C-H bond in ethanol and hydrocarbon molecules was calculated and the C-H active sites most likely to be attacked by oxygen molecule were obtained. Then, the reaction barrier of oxidation initiation reaction for different molecules was compared to conclude that the barrier energy of ethanol molecule was lower than the conventional gasoline molecule. It was found that the lower energy gap between the HOMO orbital of ethanol molecule and the LUMO orbital of oxygen molecule was the driving force to the oxidation initiation reaction. In addition, the possible further reaction paths of ethanol free radical after dehydrogenation have also been investigated, which may generate acetaldehyde or acetic acid. The two reaction paths actually existed at the same time, though compared with the acetic acid steps, the reaction path was shorter for generating acetaldehyde. It was indicated that ethanol gasoline is more prone to oxidation than conventional gasoline, which leads to changes in its molecular composition and physical and chemical properties. We should pay attention to the oxidation stability of ethanol gasoline during its storage and use.},
year = {2020}
}
TY - JOUR T1 - DFT Study of Oxidation Reaction Paths for Ethanol Gasoline AU - Li Na AU - Han Lu AU - Guo Xin AU - Tao Zhiping AU - Long Jun Y1 - 2020/03/26 PY - 2020 N1 - https://doi.org/10.11648/j.jenr.20200901.17 DO - 10.11648/j.jenr.20200901.17 T2 - Journal of Energy and Natural Resources JF - Journal of Energy and Natural Resources JO - Journal of Energy and Natural Resources SP - 39 EP - 43 PB - Science Publishing Group SN - 2330-7404 UR - https://doi.org/10.11648/j.jenr.20200901.17 AB - A DFT study of oxidation reaction for ethanol molecule and representative conventional molecule in gasoline was performed. At first, the homolytic dissociation energy of the different C-H bond in ethanol and hydrocarbon molecules was calculated and the C-H active sites most likely to be attacked by oxygen molecule were obtained. Then, the reaction barrier of oxidation initiation reaction for different molecules was compared to conclude that the barrier energy of ethanol molecule was lower than the conventional gasoline molecule. It was found that the lower energy gap between the HOMO orbital of ethanol molecule and the LUMO orbital of oxygen molecule was the driving force to the oxidation initiation reaction. In addition, the possible further reaction paths of ethanol free radical after dehydrogenation have also been investigated, which may generate acetaldehyde or acetic acid. The two reaction paths actually existed at the same time, though compared with the acetic acid steps, the reaction path was shorter for generating acetaldehyde. It was indicated that ethanol gasoline is more prone to oxidation than conventional gasoline, which leads to changes in its molecular composition and physical and chemical properties. We should pay attention to the oxidation stability of ethanol gasoline during its storage and use. VL - 9 IS - 1 ER -
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