Radical−Molecule Reactions for Aromatic Growth:  A Case Study for Cyclopentadienyl and Acenaphthylene

Wang, Dong; Violi, Angela

doi:10.1021/jo061036y

Cited by 30 publications

(18 citation statements)

References 38 publications

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“…The PAHs with more than two rings may form from two-ring PAH and single-ring compounds. Acenaphthylene is a typical intermediate product that is speculated to be produced via the acetylene addition to naphthalene, and further growth of big PAHs through HACA from acenaphthylene was confirmed by Wang and Violi, who reported that the 1,2 double bond in acenaphthylene has higher reactivity than the 3,4 and 4,5 aromatic bonds, and based on this result, we can easily explain the formation of three- or four-ring PAHs (Figure a). In addition to the HACA mechanism, another pathway based on the reaction of naphthalene and cyclopentadiene is also proposed for the formation of PAHs .…”

Section: Fates Of Carbon Oxygen and Hydrogen In Biomass Pyrolysissupporting

confidence: 60%

Fates of Chemical Elements in Biomass during Its Pyrolysis

et al. 2017

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Biomass is increasingly perceived as a renewable resource rather than as an organic solid waste today, as it can be converted to various chemicals, biofuels, and solid biochar using modern processes. In the past few years, pyrolysis has attracted growing interest as a promising versatile platform to convert biomass into valuable resources. However, an efficient and selective conversion process is still difficult to be realized due to the complex nature of biomass, which usually makes the products complicated. Furthermore, various contaminants and inorganic elements (e.g., heavy metals, nitrogen, phosphorus, sulfur, and chlorine) embodied in biomass may be transferred into pyrolysis products or released into the environment, arousing environmental pollution concerns. Understanding their behaviors in biomass pyrolysis is essential to optimizing the pyrolysis process for efficient resource recovery and less environmental pollution. However, there is no comprehensive review so far about the fates of chemical elements in biomass during its pyrolysis. Here, we provide a critical review about the fates of main chemical elements (C, H, O, N, P, Cl, S, and metals) in biomass during its pyrolysis. We overview the research advances about the emission, transformation, and distribution of elements in biomass pyrolysis, discuss the present challenges for resource-oriented conversion and pollution abatement, highlight the importance and significance of understanding the fate of elements during pyrolysis, and outlook the future development directions for process control. The review provides useful information for developing sustainable biomass pyrolysis processes with an improved efficiency and selectivity as well as minimized environmental impacts, and encourages more research efforts from the scientific communities of chemistry, the environment, and energy.

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Section: Fates Of Carbon Oxygen and Hydrogen In Biomass Pyrolysissupporting

confidence: 60%

Fates of Chemical Elements in Biomass during Its Pyrolysis

et al. 2017

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“…Thermochemical parameters, such as enthalpy and Gibbs free energy were calculated using highly accurate composite methods, such as CBS‐QB3 and G3B3 methods. Earlier studies reported that CBS‐QB3 and G3B3 methods will provide better thermochemical results with in chemical accuracy (ie, within 3‐5 kcal/mol) . For all the reactive species, T1 diagnostic values are calculated using CCSD(T)/cc‐pVTZ method.…”

Section: Computational Detailsmentioning

confidence: 99%

Hydrolysis of HNSO₂: A potential route for atmospheric production of H₂SO₄ and NH₃

Manonmani

Sandhiya

Senthilkumar

2020

Int J of Quantum Chemistry

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The hydrolysis of sulfonylamine (HNSO 2 ) results in the formation of sulfuric acid along with ammonia, and is of significant interest due to their negative impact on environment and life on Earth. The formation of H 2 SO 4 through the reaction of HNSO 2 with (H 2 O) [2][3][4] has been studied using high level electronic structure calculations. This hydrolysis reaction is a step-wise process, in the first step a H-atom from H 2 O is transferred to the N-atom of HNSO 2 which results in the formation of NH 2 , and in the next step, H 2 SO 4 , NH 3 and water molecule(s) are formed. The results show that the energy barrier associated with the formation of intermediates and product complexes is reduced by 7 to 10 kcal/mol when the number of water molecules is increased from 2 to 4. The rate constant was calculated using canonical variational transition state theory with small curvature tunneling correction over the temperature range of 200 to 1000 K. At 298 K, the calculated rate constant for the formation of intermediate in the first step is 2.24 × 10 −16 , 1.03 × 10 −12 , and 2.10 × 10 −11 cm 3 mol −1 s −1 , respectively, for the reaction with water dimer, trimer and tetramer. The calculated enthalpy and free energy show that the reaction corresponding to the formation of H 2 SO 4 is highly exothermic and exoergic in nature. K E Y W O R D Skinetics, sulfonylamine, sulfuric acid, water dimer, water tetramer, water trimer, aereosol, atmospheric reaction

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“…It was reported that further growth of large PAH via HACA from acenaphthylene was possible (Shulka and Koshi, 2012). Wang and Violi (2006) reported that the 1,2 double bond in acenaphthylene is much more reactive than the 3,4 and 4,5 aromatic bonds, based on which it is easy to explain the formation of fluoranthene, as shown in The formation of a new six-member ring via this mechanism can account for ~25% of the total product yield, whereas the remaining ~75% of the products are CP-PAH molecules formed via a five-member ring closure involving the same ethynyl and ethenyl groups (Kislov et al, 2013). Richter and Howard (2000) and Marsh and Wornat (2000) also reported that it is unlikely to produce phenanthrene from naphthalene via HACA.…”

Section: Mechanism Of Pah Growthmentioning

confidence: 99%

Polycyclic aromatic hydrocarbons (PAH) formation from the pyrolysis of different municipal solid waste fractions

et al. 2015

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The formation of 2-4 ring polycyclic aromatic hydrocarbons (PAH) from the pyrolysis of nine different municipal solid waste fractions (xylan, cellulose, lignin, pectin, starch, polyethylene (PE), polystyrene (PS), polyvinyl chloride (PVC), and polyethylene terephthalate (PET)) were investigated in a fixed bed furnace at 800 °C. The mass distribution of pyrolysis was also reported. The results showed that PS generated the most total PAH, followed by PVC, PET, and lignin. More PAH were detected from the pyrolysis of plastics than the pyrolysis of biomass. In the biomass group, lignin generated more PAH than others. Naphthalene was the most abundant PAH, and the amount of 1-methynaphthalene and 2-methynaphthalene was also notable.Phenanthrene and fluorene were the most abundant 3-ring PAH, while benzo[a]anthracene and chrysene were notable in the tar of PS, PVC, and PET. 2-ring PAH dominated all tar samples, and varied from 40 wt.% to 70 wt.%. For PS, PET and lignin, PAH may be generated directly from the aromatic structure of the feedstock.

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Radical−Molecule Reactions for Aromatic Growth: A Case Study for Cyclopentadienyl and Acenaphthylene

Cited by 30 publications

References 38 publications

Fates of Chemical Elements in Biomass during Its Pyrolysis

Fates of Chemical Elements in Biomass during Its Pyrolysis

Hydrolysis of HNSO₂: A potential route for atmospheric production of H₂SO₄ and NH₃

Polycyclic aromatic hydrocarbons (PAH) formation from the pyrolysis of different municipal solid waste fractions

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Radical−Molecule Reactions for Aromatic Growth: A Case Study for Cyclopentadienyl and Acenaphthylene

Cited by 30 publications

References 38 publications

Fates of Chemical Elements in Biomass during Its Pyrolysis

Fates of Chemical Elements in Biomass during Its Pyrolysis

Hydrolysis of HNSO2: A potential route for atmospheric production of H2SO4 and NH3

Polycyclic aromatic hydrocarbons (PAH) formation from the pyrolysis of different municipal solid waste fractions

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Hydrolysis of HNSO₂: A potential route for atmospheric production of H₂SO₄ and NH₃