Ab-initio studies of thermal unimolecular decomposition of furan: A complementary deterministic and stochastic master equation model

V.‐T., Tam; Chuang, Yao-Yuan; Giri, Binod Raj; Huynh, Lam K.

doi:10.1016/j.fuel.2019.116492

Cited by 15 publications

(9 citation statements)

References 103 publications

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“…The energies needed for P6 and F-P6 formation are 77.00 and 73.96 kcal/mol at 0 K, respectively. This pathway of furan was first suggested by Vasiliou et al; however, it was found to be insignificant by later studies. − Sendt et al further proposed the mechanism of CH 3 CCH → C 3 H 3 * + H*, which resonates well with recent works by Cheng et al and Weber et al who pointed out that C 3 H 3 * is mainly formed from C 3 H 4 isomers rather than from furan directly. Nevertheless, we include this pathway in the dominating pathways of thiophene, and the relative importance will be discussed in our following kinetic studies.…”

Section: Resultssupporting

confidence: 52%

“…The formation of the thioformyl radical (HCS*, P6) from IM2 is endothermic by 72.03 kcal/mol at 0 K. However, the cracking of F-IM2 to formyl radical (HCO*) demands 69.39 kcal/mol at 0 K. When relative to the initial reactant, furan → F-P6 is 23.95 kcal/mol thermodynamically favored than thiophene → P6. The formation of HCS*/HCO* has been confirmed in the pyrolysis experiment. ,, However, the amount of HCO* produced in furan pyrolysis is negligible. ,, As no experimental data on the importance of HCS* in thiophene pyrolysis have been reported, we include this pathway in the thiophene major mechanism, and the relative importance will be discussed in our following kinetic studies.…”

Section: Resultsmentioning

confidence: 91%

“…Despite these studies, the detailed pyrolysis mechanism of thiophene remains unclear. By contrast, the unimolecular thermal decomposition mechanism of furan has been well established by both experiments − and theoretical calculations. − A rigorous theoretical investigation on the unimolecular pyrolysis of thiophene is still desirable. Hence, we conducted a comparative study on the unimolecular pyrolysis mechanism of thiophene and furan using high-level ab initio methods.…”

Section: Introductionmentioning

confidence: 99%

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Unimolecular Pyrolysis Mechanism of Thiophene and Furan: An Ab Initio Comparative Study

Hong-liang

et al. 2021

Energy Fuels

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Thiophene sulfur is the most stable and abundant organic sulfur species in petroleum. In this work, the unimolecular pyrolysis mechanism of thiophene was investigated using high-level ab initio methods. As a contrast, similar reactions of furan were computed using the same methods. It was found that the most likely initiation reactions for thiophene unimolecular pyrolysis are 2,3-H and 3,2-H transfers. The 3,2-H shift forms buta-2,3-dienethial, which subsequently decomposes to CS + CH 3 C 2 H and HC 2 CH 2 radical (*) + HCS*, whereas the 2,3-H migration corresponds to α-carbene and ultimately leads to C

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Section: Resultssupporting

confidence: 52%

Section: Resultsmentioning

confidence: 91%

Section: Introductionmentioning

confidence: 99%

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Unimolecular Pyrolysis Mechanism of Thiophene and Furan: An Ab Initio Comparative Study

Hong-liang

et al. 2021

Energy Fuels

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“…Finally, these compounds can be used in several applications, such as chemical production, fungicide propiconazole, fuel, cleaners, pharmaceuticals, etc. [43,44]. As shown in GC-MS analysis, at the lowest heating rate (5 • C/min), Propene, 1-Propene, 2-methyl-, Pentane, 2,4-Dimethyl-1-heptene compounds were the most abundant pyrolysis compounds in the released volatile products from the sample free of ZSM-5.…”

Section: Chemical Analysis Of the Synthesized Chemical Compounds Using Gc-msmentioning

confidence: 79%

“…In addition, strong presence of other compounds generated from the catalytic pyrolysis of ZSM-5 were typical energy products. Finally, these compounds can be used in several applications, such as chemical production, fungicide propiconazole, fuel, cleaners, pharmaceuticals, etc., [43,44].…”

Section: Chemical Analysis Of the Synthesized Chemical Compounds Using Gc-msmentioning

confidence: 99%

Catalytic Pyrolysis Kinetic Behavior and TG-FTIR-GC–MS Analysis of Metallized Food Packaging Plastics with Different Concentrations of ZSM-5 Zeolite Catalyst

et al. 2021

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Recently, the pyrolysis process has been adapted as a sustainable strategy to convert metallized food packaging plastics waste (MFPW) into energy products (paraffin wax, biogas, and carbon black particles) and to recover aluminum. Usually, catalysts are used in pyrolysis treatment to refine pyrolysis products and to increase their yield. In order to study the effect of a catalyst on the formulated volatile products, this work aims to study the pyrolysis behavior of MFPW in presence of catalyst, using TG-FTIR-GC–MS system. The pyrolysis experiments were conducted with ZSM-5 Zeolite catalyst with different concentrations (10, 30, and 50 wt.%) at different heating rates (5, 10, 15, 20, 25, and 30 °C/min). In addition, TG-FTIR system and GC-MS unit were used to observe and analyze the thermal and chemical degradation of the obtained volatile compounds at maximum decomposition peaks. In addition, the kinetic results of catalytic pyrolysis of ZSM-5/MFPW samples matched when model-free methods, a distributed activation energy model (DAEM), and an independent parallel reaction kinetic model (IPR) were used. The TGA-DTG results showed that addition of a catalyst did not have a significant effect on the features of the TGA-DTG curves with similar weight loss of 87–90 wt.% (without taking the weight of the catalyst into account). Meanwhile, FTIR results manifested strong presence of methane and high-intensity functional group of carboxylic acid residues, especially at high concentration of ZSM-5 and high heating rates. Likewise, GC-MS measurements showed that Benzene, Toluene, Hexane, p-Xylene, etc. compounds (main flammable liquid compounds in petroleum oil) generated catalysts exceeding 50%. Finally, pyrolysis kinetics showed that the whole activation energies of catalytic pyrolysis process of MFPW were estimated at 289 kJ/mol and 110, 350, and 174 kJ/mol for ZSM-5/MFPW samples (10, 30, and 50 wt.%, respectively), whereas DAEM and IPR approaches succeeded to simulate TGA and DTG profiles with deviations below <1.

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Thermal unimolecular decomposition of ethyl 2‐furoate and its reactivity toward OH radicals: A theoretical study

V.‐T.

Lin

Huynh

2020

Int J of Chemical Kinetics

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Mechanism and kinetics of the thermal pyrolysis of ethyl 2‐furoate were studied in a wide range of conditions (ie, 500‐1500 K and 1‐7600 Torr) using the accurate dual‐level theory CCSD(T)&MP2(FC)//B3LYP/aug‐cc‐pVTZ and state‐of‐the‐art Rice‐Ramsperger‐Kassel‐Marcus based master equation rate model including hindered internal rotation and tunneling treatments. The predicted rate coefficients are found to be in accordance with the experimental data. The mechanism details are revealed as (i) the major decomposition channel occurs via a six‐center transition state with the barrier energy of 48.3 kcal/mol at 0 K, leading to the formation of C2H4 and 2‐furoic acid and (ii) pressure has a slightly positive effect on the rate constant, particularly at the high temperature. Also, the reactivity of ethyl 2‐furoate toward OH radicals was discussed in the first place.

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Ab-initio studies of thermal unimolecular decomposition of furan: A complementary deterministic and stochastic master equation model

Cited by 15 publications

References 103 publications

Unimolecular Pyrolysis Mechanism of Thiophene and Furan: An Ab Initio Comparative Study

Unimolecular Pyrolysis Mechanism of Thiophene and Furan: An Ab Initio Comparative Study

Catalytic Pyrolysis Kinetic Behavior and TG-FTIR-GC–MS Analysis of Metallized Food Packaging Plastics with Different Concentrations of ZSM-5 Zeolite Catalyst

Thermal unimolecular decomposition of ethyl 2‐furoate and its reactivity toward OH radicals: A theoretical study

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