Understanding the reactivity of unsaturated alcohols: Experimental and kinetic modeling study of the pyrolysis and oxidation of 3-methyl-2-butenol and 3-methyl-3-butenol

Bruycker, Ruben De; Herbinet, Olivier; Carstensen, Hans-Heinrich; Battin‐Leclerc, Frédérique; Geem, Kevin Van

doi:10.1016/j.combustflame.2016.06.009

Cited by 27 publications

(43 citation statements)

References 78 publications

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“…Following initial branching reactions, both fuels produce an array of butenes, which can subsequently form propene and other low-molecular weight intermediates, prior to the final CO 2 and H 2 O equilibrium 99 , 100 . As there appears to be an extensive reliance on the tert-butyl radical chemistry in DIB combustion, it would be appropriate to include this chemistry to other existing mechanisms, such as that of Yasunaga et al 101 , and De Bruycker et al 102 . Of particular importance for DIB combustion is the ability of isobutylene to interact with methyl or methylene radicals as shown in R26 and R27.…”

Section: Resultsmentioning

confidence: 99%

Elucidating the differences in oxidation of high-performance α- and β- diisobutylene biofuels via Synchrotron photoionization mass spectrometry

Terracciano

Neupane

Popolan-Vaida

et al. 2020

Sci Rep

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Biofuels are a promising ecologically viable and renewable alternative to petroleum fuels, with the potential to reduce net greenhouse gas emissions. However, biomass sourced fuels are often produced as blends of hydrocarbons and their oxygenates. Such blending complicates the implementation of these fuels in combustion applications. Variations in a biofuel’s composition will dictate combustion properties such as auto ignition temperature, reaction delay time, and reaction pathways. A handful of novel drop-in replacement biofuels for conventional transportation fuels have recently been down selected from a list of over 10,000 potential candidates as part of the U.S. Department of Energy’s (DOE) Co-Optimization of Fuels and Engines (Co-Optima) initiative. Diisobutylene (DIB) is one such high-performing hydrocarbon which can readily be produced from the dehydration and dimerization of isobutanol, produced from the fermentation of biomass-derived sugars. The two most common isomers realized, from this process, are 2,4,4-trimethyl-1-pentene (α-DIB) and 2,4,4-trimethyl-2-pentene (β-DIB). Due to a difference in olefinic bond location, the α- and β- isomer exhibit dramatically different ignition temperatures at constant pressure and equivalence ratio. This may be attributed to different fragmentation pathways enabled by allylic versus vinylic carbons. For optimal implementation of these biofuel candidates, explicit identification of the intermediates formed during the combustion of each of the isomers is needed. To investigate the combustion pathways of these molecules, tunable vacuum ultraviolet (VUV) light (in the range 8.1–11.0 eV) available at the Lawrence Berkeley National Laboratory’s Advanced Light Source (ALS) has been used in conjunction with a jet stirred reactor (JSR) and time-of-flight mass spectrometry to probe intermediates formed. Relative intensity curves for intermediate mass fragments produced during this process were obtained. Several important unique intermediates were identified at the lowest observable combustion temperature with static pressure of 93,325 Pa and for 1.5 s residence time. As this relatively short residence time is just after ignition, this study is targeted at the fuels’ ignition events. Ignition characteristics for both isomers were found to be strongly dependent on the kinetics of C4 and C7 fragment production and decomposition, with the tert-butyl radical as a key intermediate species. However, the ignition of α-DIB exhibited larger concentrations of C4 compounds over C7, while the reverse was true for β-DIB. These identified species will allow for enhanced engineering modeling of fuel blending and engine design.

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Section: Resultsmentioning

confidence: 99%

Elucidating the differences in oxidation of high-performance α- and β- diisobutylene biofuels via Synchrotron photoionization mass spectrometry

Terracciano

Neupane

Popolan-Vaida

et al. 2020

Sci Rep

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“…Van Geem et al studied the pyrolysis and oxidation of 3-methyl-2-butenol and 3methyl-3-butenol (two isomers of MBO232) using an isothermal jet-stirred quartz reactor at 500−1100 K and 1 atm. 10 The OH radical is a widely studied species in combustion chemistry due to its abundance in flame. In the literature, OH reaction kinetics at around 800−1300 K have been widely studied by shock tube experiments.…”

Section: Introductionmentioning

confidence: 99%

“…Although a lot of studies have been conducted on the combustion of alcohols, − a majority of them focused on saturated alcohols, and only limited studies focused on unsaturated alcohols. Recent studies show that unsaturated alcohols not only are important intermediates in combustion but also can be considered as the next-generation bio-derived fuels for spark-ignition combustion engines. , 2-Methyl-3-buten-2-ol (MBO232), a C5 unsaturated alcohol, is considered to be a potential candidate for biofuel and renewable fuel additives . MBO232 has a high energy density of 29,544 MJ/m 3 , close to that of gasoline (33,867 MJ/m 3 ) .…”

Section: Introductionmentioning

confidence: 99%

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Predictive Combustion Kinetics of OH Radical Reactions with a C5 Unsaturated Alcohol: The Competitive H-Abstraction and OH-Addition Reactions of 2-Methyl-3-buten-2-ol

Guan

Wang

et al. 2021

J. Phys. Chem. A

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2-Methyl-3-buten-2-ol (MBO232) is a potential biofuel and renewable fuel additive. In a combustion environment, the consumption of MBO232 is mainly through the reaction with a OH radical, one of the most important oxidants. Here, we predict the intricate reactions of MBO232 and OH radicals under a broad range of combustion conditions, that is, 230–2500 K and 0.01–1000 atm. The potential energy surfaces of H-abstraction and OH-addition have been investigated at the CCSD(T)/CBS//M06-2X/def2-TZVP level, and the rate constants were calculated via Rice–Ramsperger–Kassel–Marcus/master equation (RRKM/ME) theory. The decomposition reactions of the critical intermediates from the OH-addition reactions have also been studied. Our results show that OH-addition reactions are dominant below 850 K, while H-abstraction reactions, especially the channel-abstracting H atoms from the methyl groups, are more competitive at higher temperatures. We found that it is necessary to discriminate H atoms attached to the same C atom, as their abstraction rates can differ by up to 1 order of magnitude. The calculated results show good agreement with the reported experimental data. We have provided the modified Arrhenius expressions for rate constants of the dominant channels. The kinetic data determined in this work are of much value for constructing the combustion models of MBO232 and understanding the combustion kinetics and mechanism of other unsaturated alcohols.

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“…Detailed analyses of the reactivities of contracted lignin models, including ortho -quinone methide (QM), ,,, anisole, and catechol, − which are believed to be intermediates in lignin thermolysis and char formation, are available in the literature for comparisons. There are also a variety of studies on the reactions of OH radicals with simple alkenes and unsaturated model compounds such as C 2 H 4 , − acrolein (CH 2 CH–CHO), enols (albeit more focused on further combustion reactions), , styrene, aldehydes, − and unsaturated alcohols − to represent the side-chain double bond of the lignin and monolignols.…”

Section: Introductionmentioning

confidence: 99%

OH-Initiated Reactions of para-Coumaryl Alcohol Relevant to the Lignin Pyrolysis. Part II. Kinetic Analysis

et al. 2020

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Monolignols are precursor units and primary products of lignin pyrolysis. The currently available global (lumped) and semidetailed kinetic models, however, are lacking the comprehensive decomposition kinetics of these key intermediates in order to advance toward the fundamentally based detailed chemical-kinetic models of biomass pyrolysis. para-Coumaryl alcohol (HOPh−CHCH−CH 2 OH, p-CMA) is the simplest of the three basic monolignols containing a typical side-chain double bond and both alkyl and phenolic type OH groups. The two other monomers additionally contain one and two methoxy groups, respectively, attached to the benzene ring. Previously, we developed a detailed fundamentally based mechanism for unimolecular decomposition of p-CMA (as well as its truncated allyl and cinnamyl alcohol models) and explored its reactivity toward H radicals generated during pyrolysis. The reactions of p-CMA with pyrolytic OH radicals is another set of key reactions particularly important for understanding the formation mechanisms of a wide variety of oxygenates in oxygen-deficit (anaerobic) conditions and the role of the lignin side groups in pyrolysis pathways. In Part I of the current study (J. Phys. Chem. A, 2019, 123, 2570−2585), we reported a detailed potential energy (enthalpy) surface analysis of the reaction OH + p-CMA with suggestions for a variety of chemically activated, unimolecular, and bimolecular reaction pathways. In Part II of our work, we provide a detailed kinetic analysis of the major reaction channels to evaluate their significance and possible impacts on product distributions. Temperature-and pressure-dependent rate constants are calculated using the quantum Rice−Ramsperger−Kassel method and the master equation analysis for falloff and stabilization. Enthalpies of formation, entropies, and heat capacities are calculated using density functional theory and higher-level composite methods for stable molecules, radicals, and transition-state species. A significant difference between well depths for the chemically activated adduct radicals, [p-CMA-OH]*, is found for the αand β-carbon addition reactions to generate the 1,3-and 1,2-diol radicals, respectively. This is due to the synergistic effect from conjugation of the proximal radical center with the aromatic ring and the strong H-bonding interaction between vicinal OH groups in the β-adduct (1,2-diol radical). Both adducts undergo isomerization and low-energy transformations, however, with different kinetic efficiencies because of the difference in stabilization energies. Reaction pathways include dissociation, intramolecular abstraction, atom and group transfers, and elimination. Of particular interest is a roaming-like low-energy dehydration reaction to form O-centered intermediate radicals. The kinetic analysis demonstrated the feasible formation of various products detected in pyrolysis experiments, suggesting that the gas-phase reactions of OH radicals can be a key process to form major products and complex oxygenates during lignin pyrolysis. Our prelim...

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Understanding the reactivity of unsaturated alcohols: Experimental and kinetic modeling study of the pyrolysis and oxidation of 3-methyl-2-butenol and 3-methyl-3-butenol

Cited by 27 publications

References 78 publications

Elucidating the differences in oxidation of high-performance α- and β- diisobutylene biofuels via Synchrotron photoionization mass spectrometry

Elucidating the differences in oxidation of high-performance α- and β- diisobutylene biofuels via Synchrotron photoionization mass spectrometry

Predictive Combustion Kinetics of OH Radical Reactions with a C5 Unsaturated Alcohol: The Competitive H-Abstraction and OH-Addition Reactions of 2-Methyl-3-buten-2-ol

OH-Initiated Reactions of para-Coumaryl Alcohol Relevant to the Lignin Pyrolysis. Part II. Kinetic Analysis

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