Theoretical study on the reaction route for the major liquid product from pyrolysis of triethylamine

Wang, Ze; Lin, Ruisen

doi:10.1016/j.jaap.2007.11.010

Cited by 10 publications

(10 citation statements)

References 5 publications

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“…Those work confirmed the feasibility of applying initiator as an effective additive to improve heat sink of jet fuel under supercritical condition. Wang et al − also studied thermal cracking of heptane initiated by triethylamine (TEA) and tributylamine (TBA) in a flowing reactor at the temperature of 550−650 °C under atmospheric pressure and supercritical conditions. They indicated that TEA and TBA are effective in promoting the cracking rate of heptane and ascribed the accelerating effects to the initiative release of ethyl radical by TEA from the scission of the C−N bond based on GC-MS and molecular simulation results.…”

Section: Introductionmentioning

confidence: 99%

Supercritical Thermal Cracking of N-Dodecane in Presence of Several Initiative Additives: Products Distribution and Kinetics

et al. 2008

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Supercritical initiative-thermal cracking of a jet fuel model compound, n-dodecane, was studied in presence of several initiative additives, such as1-nitropropane (NP), triethylamine (TEA), and 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonane (TEMPO) in view of improving heat sink of jet fuel. It was found that remarkable promoting effect of the initiative additives on the cracking rates, compared with the thermal cracking of pure n-dodecane, were observed up to 20-150% in the following order: NP > TEMPO > TEA. Comparisons of products distributions from the thermal cracking of n-dodecane with and without initiators indicated that initiators type had a slight effect on the gas products selectivity, but a non-negligible effect on liquid products distributions. Apparent first-order kinetics was used to describe the supercritical initiative-thermal cracking of n-dodecane, and the apparent cracking activation energy of pure n-dodecane were 256.56 kJ/mol, which decreased to 185.80 kJ/mol by NP, 196.05 kJ/mol by TEMPO, and 242.83 kJ/mol by TEA. Attempts were also made to explain the observed experimental results with proposed reaction mechanisms for the thermal cracking of pure initiators.

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Section: Introductionmentioning

confidence: 99%

Supercritical Thermal Cracking of N-Dodecane in Presence of Several Initiative Additives: Products Distribution and Kinetics

et al. 2008

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“…These values can be compared to those obtained by Wang and Lin on triethylamine ((CH 3 CH 2 ) 3 -N) presented in Figure . It can be seen that both results show similar trends for comparable bonds.…”

Section: Chemical Kinetic Model Developmentmentioning

confidence: 99%

“…Wang et al concluded that under their conditions, the initial C–N bond fission in TEA is preponderant. In a subsequent theoretical study, Wang and Lin performed theoretical calculations to understand the initiation of triethylamine.…”

Section: Introductionmentioning

confidence: 99%

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Kinetic Modeling of the Thermal Destruction of Nitrogen Mustard Gas

Lizardo-Huerta

Sirjean

Verdier³

et al. 2017

J. Phys. Chem. A

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The destruction of stockpiles or unexploded ammunitions of nitrogen mustard (tris(2-chloroethyl)amine, HN-3) requires the development of safe processes. The thermal destruction of this kind of compound is one of the most efficient method of destruction. Because of the high-level of toxicity of this chemical, there is a considerable lack of knowledge on the chemical kinetics at high temperatures. In this study, a detailed chemical kinetic model for the pyrolysis of nitrogen mustard gas is developed based on a large number of thermokinetic parameters calculated with theoretical chemistry. The thermal decomposition of HN-3 is shown to mainly proceed through stepwise dechlorination with Cl-atom being the principal chain carrier. The successive losses of chlorine atom mainly lead to unsaturated amines without chlorine groups. Theoretical calculations demonstrated that the thermal decomposition of these compounds ultimately lead to the formation of pyrrole, which can accumulate at low temperature. At higher temperatures, pyrrole yields HCN and acetylene. Simulations also predict that about 52% of the total flux of decomposition of HN-3 leads to the formation of N,N-diethenyl-2-chloroethylamine (P29), which acts as a chain branching agent because its unimolecular decomposition is preponderant and produces one chlorine and one hydrogen atoms. Comparisons with the simulated reactivity of sulfur mustard gas are also performed and show that HN-3 is more reactive that the former toxic. The higher number of chlorine atoms in HN-3 compared to sulfur mustard (3 vs 2) and the formation of the chain branching intermediate P29 during its decomposition explain this behavior.

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“…In recent years, many studies have been performed in this particular area. The improvement effect of initiators on the heat sink capacity − and conversion rate ,− of fuel were studied experimentally. These previous experimental results demonstrated that initiators could improve the heat sink capacity and greatly accelerate the reaction rate of jet fuel.…”

Section: Introductionmentioning

confidence: 99%

Experimental Investigation on Pyrolysis of n-Decane Initiated by Nitropropane under Supercritical Pressure in a Miniature Tube

Jia

Zhou

et al. 2019

Energy Fuels

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Adding an initiator is an effective method of promoting hydrocarbon pyrolysis and improving the heat sink of fuels. Nitropropane was proposed as an initiator with good performance, owing to its lower reaction activation energy for C–N bond cleavage. To study the effects of this initiator on hydrocarbon pyrolysis, a miniature tube reactor that can simulate a real heating procedure in an aeroengine was used to investigate the n-decane pyrolysis with and without nitropropane under experimental supercritical conditions. The results demonstrate that the nitropropane initiator promotes the pyrolysis of fuel as it flows through a tube with a large length–diameter ratio within a certain temperature range. The initial decomposition temperature of n-decane is reduced by approximately 100 K, and the increase in the conversion leads to a higher heat sink for n-decane, which can result in decreases in the fuel and reactor temperatures under the same heating condition and within the effective temperature range. A stronger promoting effect can be achieved by increasing the concentration of the nitropropane initiator. The variation laws for the n-decane pyrolysis reaction rate along the flow reactor are changed by the initiator, the presence of nitropropane greatly accelerates the pyrolysis reaction of fuel at a lower temperature, and the opposite tendency appears as the fuel temperature increases, which is caused by the consumption of the initiator. In addition, the selectivity of methane, propane, and alkenes, especially ethylene, increases because of the propyl radical generated by the C–N dissociation of nitropropane before the initiator is consumed.

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Theoretical study on the reaction route for the major liquid product from pyrolysis of triethylamine

Cited by 10 publications

References 5 publications

Supercritical Thermal Cracking of N-Dodecane in Presence of Several Initiative Additives: Products Distribution and Kinetics

Supercritical Thermal Cracking of N-Dodecane in Presence of Several Initiative Additives: Products Distribution and Kinetics

Kinetic Modeling of the Thermal Destruction of Nitrogen Mustard Gas

Experimental Investigation on Pyrolysis of n-Decane Initiated by Nitropropane under Supercritical Pressure in a Miniature Tube

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