Analysis of pyrolysis products from light hydrocarbons and kinetic modeling for growth of polycyclic aromatic hydrocarbons with detailed chemistry

Norinaga, Koyo; Deutschmann, Olaf; Saegusa, Naomichi; Hayashi, Jun Ichiro

doi:10.1016/j.jaap.2009.05.001

Cited by 94 publications

(90 citation statements)

References 36 publications

(63 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[1][2][3][4] In recent years, such reaction networks have been used in various areas such as steam cracking of hydrocarbons, 4 combustion processes, 5,6 and the formation of polycyclic aromatic hydrocarbons. [7][8][9] Current interests in the thermochemical conversion of biomass to liquid fuels or commodity chemicals leads to the need for kinetic models that describe the pyrolysis of its components cellulose, hemicellulose, and lignin. The decomposition of lignin yields mainly substituted monocyclic aromatic compounds with substituent groups such as hydroxy (AOH), methoxy (AOCH 3 ), formyl (ACHO), vinyl (AC@CH 2 ), and alkyl (AR).…”

Section: Introductionmentioning

confidence: 99%

First‐principles based group additivity values for thermochemical properties of substituted aromatic compounds

et al. 2015

View full text Add to dashboard Cite

A set of 7 Benson group additive values (GAV) together with 15 correction terms for non-nearest neighbor interactions (NNI) is developed to calculate the gas phase standard enthalpies of formation, entropies and heat capacities of monocyclic aromatic compounds containing methyl, ethyl, vinyl, formyl, hydroxyl, and methoxy substituents. These GAVs are obtained through least squares regression of a database of thermodynamic properties of 143 molecules, calculated at the post-Hartree-Fock G4 composite method. Out of the 15 NNIs, which account for several well-known substituent effects in aromatic molecules, 13 have been determined for the first time. All but two group additively calculated standard enthalpies of formation agree within 4 kJ mol 21. The entropies and the heat capacities generally deviate less than 4 J mol 21 K 21 from the ab initio results. Natural bond orbital analysis is utilized to identify the underlying causes of the observed NNIs.

show abstract

Section: Introductionmentioning

confidence: 99%

First‐principles based group additivity values for thermochemical properties of substituted aromatic compounds

et al. 2015

View full text Add to dashboard Cite

show abstract

“…Formation of soot in the regions of combustors with locally fuel rich areas is accompanied by the formation of polycyclic aromatic hydrocarbons (PAHs), which can be considered as soot precursors via the hydrogen abstraction-acetylene addition (HACA) mechanism [1][2][3]. Soot particles from combustion processes are known to be associated to highly carcinogenic and mutagenic compounds such as PAH, which are present at the gas exhaust, but can also appear adsorbed on the surface of soot [4][5][6].…”

Section: Introductionmentioning

confidence: 99%

Quantification of polycyclic aromatic hydrocarbons (PAHs) found in gas and particle phases from pyrolytic processes using gas chromatography–mass spectrometry (GC–MS)

Sánchez¹,

Salafranca²,

Callejas³

et al. 2013

Fuel

View full text Add to dashboard Cite

h i g h l i g h t s " A methodology for PAH quantification from thermochemical processes was developed. " Quantification of both PAH adsorbed on soot and at the gas phase was considered. " The method gives reliable results of PAH from complex samples like soot.g r a p h i c a l a b s t r a c t . a b s t r a c tThe outlet stream from combustion processes is a complex mixture of compounds which depends on the specific operating conditions. Thermochemical processes operating under rich fuel conditions enhance the formation of polycyclic aromatic hydrocarbons (PAHs) and soot. PAH play an important role in soot formation, but they can appear adsorbed on soot surface as well as at the gas phase due to their different volatility and molecular weight. Both PAH (the gas phase and adsorbed PAH) fractions are important when considering the total characterization from pyrolytic processes, mainly for determining the emission levels of 16 Environmental Protection Agency (EPA) priority PAH. In this way, an optimized method capable to determine the aromatic compounds in the gas and particle phases in combustion exhaust gases is needed. The method here presented allows the collection and quantification of both the PAH adsorbed on soot and present at the gas phase of the exhaust gases of thermochemical processes. It involves PAH characterization by combining classical Soxhlet extraction of the sample collected, followed by an extract concentration using a rotary evaporator and subsequent micro-concentration under gentle nitrogen stream before the analysis. The EPA-PAH were determined using a gas chromatograph-mass spectrometer (GC-MS). Validation tests using a fully characterized soot, the NIST (National Institute of Standards and Technology) reference material SRM 1650b, and repeatability using diesel surrogate commercial soot named Printex-U, were done. Additionally, experiments of acetylene pyrolysis were carried out and their products analyzed for determining the PAH amount. The results showed good method 0016-2361/$ -see front matter Ó

show abstract

“…C 3 -C 4 species reactions were obtained from Hidaka's mechanism [24] and Tsang's mechanism [25]. Mechanisms for polycyclic aromatic hydrocarbons obtained from mechanisms proposed by Richter et al [26] and Norinaga et al [18] were also included to form an integrity model.…”

Section: Reaction Mechanismmentioning

confidence: 99%

“…Norinaga et al [17,18] studied the detailed kinetic modeling mechanism of light hydrocarbons (ethylene, acetylene, and propylene) in the CVD of carbon. The mechanism consisted of 241 species and 902 reactions, which gave fairly well concentration predictions and growth paths of hydrogen, small hydrocarbons, aromatic hydrocarbons, and polycyclic aromatic hydrocarbons in a vertical flow reactor at low pressures.…”

Section: Introductionmentioning

confidence: 99%

A molecular-level analysis of gas-phase reactions in chemical vapor deposition of carbon from methane using a detailed kinetic model

Zhang

et al. 2016

J Mater Sci

View full text Add to dashboard Cite

This work describes a modeling study of methane pyrolysis in chemical vapor deposition (CVD). The model consists of a detailed chemical kinetic model, which includes 241 species and 909 gas-phase reactions for methane pyrolysis mechanism, and a plug-flow model, which describes the transport conditions in CVD. Reasonably good agreements were obtained between the simulation results and the experimental results of methane pyrolysis in CVD of pyrocarbon in a vertical hot-wall deposition reactor without any artificial adjustments. The mole fractions of hydrogen, acetylene, ethylene, and benzene increased with a decreasing growth rate as the residence time and the initial methane pressure increased. Sensitivity analysis and reaction paths were conducted to identify the crucial reaction steps and explain how they impact in this pyrolysis process. Results showed that methane pyrolysis had an incubation stage to form a necessary gas atmosphere for the pyrolysis to move forward and C 3 species were the main direct source for benzene formation. These results should be useful to understand methane pyrolysis at a molecular level in CVD, as well as the relationship between the gas species and the pyrocarbon.

show abstract

Analysis of pyrolysis products from light hydrocarbons and kinetic modeling for growth of polycyclic aromatic hydrocarbons with detailed chemistry

Cited by 94 publications

References 36 publications

First‐principles based group additivity values for thermochemical properties of substituted aromatic compounds

First‐principles based group additivity values for thermochemical properties of substituted aromatic compounds

Quantification of polycyclic aromatic hydrocarbons (PAHs) found in gas and particle phases from pyrolytic processes using gas chromatography–mass spectrometry (GC–MS)

A molecular-level analysis of gas-phase reactions in chemical vapor deposition of carbon from methane using a detailed kinetic model

Contact Info

Product

Resources

About