Gas phase pyrolysis of heterocyclic compounds, part 3. Flow pyrolysis and annulation reactions of some nitrogen heterocycles. A product oriented study

Winkler, Jens K; Karow, Werner; Rademacher, Paul

doi:10.3998/ark.5550190.0001.410

Cited by 10 publications

(2 citation statements)

References 18 publications

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“…The production of H atoms via C–H bond cleavage is the initiation step in the thermal decomposition mechanism of aromatic ring compounds such as benzene, , naphthalene, , and many others. There are also six-member aromatic rings containing nitrogen, such as pyridine, picoline, quinoline, and isoquinoline that are also responsible for the production of hydrogen atoms. − …”

Section: Introductionmentioning

confidence: 99%

A Deep Insight into the Details of the Interisomerization and Decomposition Mechanism of o-Quinolyl and o-Isoquinolyl Radicals. Quantum Chemical Calculations and Computer Modeling

2016

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The isomerization of o-quinolyl ↔ o-isoquinolyl radicals and their thermal decomposition were studied by quantum chemical methods, where potential energy surfaces of the reaction channels and their kinetics rate parameters were determined. A detailed kinetics scheme containing 40 elementary steps was constructed. Computer simulations were carried out to determine the isomerization mechanism and the distribution of reaction products in the decomposition. The calculated mole percent of the stable products was compared to the experimental values that were obtained in this laboratory in the past, using the single pulse shock tube. The agreement between the experimental and the calculated mole percents was very good. A map of the figures containing the mole percent's of eight stable products of the decomposition plotted vs T are presented. The fast isomerization of o-quinolyl → o-isoquinolyl radicals via the intermediate indene imine radical and the attainment of fast equilibrium between these two radicals is the reason for the identical product distribution regardless whether the reactant radical is o-quinolyl or o-isoquinolyl. Three of the main decomposition products of o-quinolyl radical, are those containing the benzene ring, namely, phenyl, benzonitrile, and phenylacetylene radicals. They undergo further decomposition mainly at high temperatures via two types of reactions: (1) Opening of the benzene ring in the radicals, followed by splitting into fragments. (2) Dissociative attachment of benzonitrile and phenyl acetylene by hydrogen atoms to form hydrogen cyanide and acetylene.

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Section: Introductionmentioning

confidence: 99%

A Deep Insight into the Details of the Interisomerization and Decomposition Mechanism of o-Quinolyl and o-Isoquinolyl Radicals. Quantum Chemical Calculations and Computer Modeling

2016

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“…A similar methodology implementing the FID and the NPD was applied to analyze the shale oil pyrolysis products in a continuous flow reactor 8 . Using a cold trap at 273.15 K and GC-MS, Winkler et al 33 showed that during pyridine pyrolysis heteroatom-containing aromatic compounds are formed.…”

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confidence: 99%

On-line Analysis of Nitrogen Containing Compounds in Complex Hydrocarbon Matrixes

Ristic

Djokic

Marin

2016

JoVE

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The shift to heavy crude oils and the use of alternative fossil resources such as shale oil are a challenge for the petrochemical industry. The composition of heavy crude oils and shale oils varies substantially depending on the origin of the mixture. In particular they contain an increased amount of nitrogen containing compounds compared to the conventionally used sweet crude oils. As nitrogen compounds have an influence on the operation of thermal processes occurring in coker units and steam crackers, and as some species are considered as environmentally hazardous, a detailed analysis of the reactions involving nitrogen containing compounds under pyrolysis conditions provides valuable information. Therefore a novel method has been developed and validated with a feedstock containing a high nitrogen content, i.e., a shale oil. First, the feed was characterized offline by comprehensive two-dimensional gas chromatography (GC × GC) coupled with a nitrogen chemiluminescence detector (NCD). In a second step the on-line analysis method was developed and tested on a steam cracking pilot plant by feeding pyridine dissolved in heptane. The former being a representative compound for one of the most abundant classes of compounds present in shale oil. The composition of the reactor effluent was determined via an in-house developed automated sampling system followed by immediate injection of the sample on a GC × GC coupled with a time-of-flight mass spectrometer (TOF-MS), flame ionization detector (FID) and NCD. A novel method for quantitative analysis of nitrogen containing compounds using NCD and 2-chloropyridine as an internal standard has been developed and demonstrated.

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Quantum Chemistry Study on the Pyrolysis Mechanisms of Coal‐Related Model Compounds

Wang¹,

Zhang²,

Ling³

2011

Rate Constant Calculation for Thermal Reactions

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Gas phase pyrolysis of heterocyclic compounds, part 3. Flow pyrolysis and annulation reactions of some nitrogen heterocycles. A product oriented study

Cited by 10 publications

References 18 publications

A Deep Insight into the Details of the Interisomerization and Decomposition Mechanism of o-Quinolyl and o-Isoquinolyl Radicals. Quantum Chemical Calculations and Computer Modeling

A Deep Insight into the Details of the Interisomerization and Decomposition Mechanism of o-Quinolyl and o-Isoquinolyl Radicals. Quantum Chemical Calculations and Computer Modeling

On-line Analysis of Nitrogen Containing Compounds in Complex Hydrocarbon Matrixes

Quantum Chemistry Study on the Pyrolysis Mechanisms of Coal‐Related Model Compounds

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