Abstract
The reaction pathways leading to aromatic hydrocarbons such as benzene and naphthalene in gas-phase reactions of multi-component mixtures derived from cellulose fast pyrolysis were studied both experimentally and numerically. A two-stage tubular reactor was used for evaluating the reaction kinetics of secondary vapor phase cracking of the nascent pyrolysates at temperature ranging from 400 to 900°C, residence time from 0.2 to 4.3s, and at 241kPa. The products of alkyne and diene were identified from the primary pyrolysis of cellulose even at low temperature range 500-600°C. These products include acetylene, propyne, propadiene, vinylacetylene, and cyclopentadiene. Experiments were also numerically validated by a detailed chemical kinetic model consisting of more than 8000 elementary step-like reactions with over 500 chemical species. Acceptable capabilities of the kinetic model in predicting concentration profiles of the products enabled us to assess reaction pathways leading to benzene and naphthalene via the alkyne and diene from primary pyrolysates of cellulose. C3 alkyne and diene are primary precursors of benzene at 650°C, while combination of ethylene and vinylacetylene produces benzene dominantly at 850°C. Cyclopentadiene is a prominent precursor of naphthalene. Combination of acetylene with propyne or allyl radical leads to the formation of cyclopentadiene. Furan and acrolein are likely important alkyne precursors in cellulose pyrolysis at low temperature, whereas dehydrogenations of olefins are major route to alkyne at high temperatures.
| Original language | English |
|---|---|
| Pages (from-to) | 144-154 |
| Number of pages | 11 |
| Journal | Biomass and Bioenergy |
| Volume | 69 |
| DOIs | |
| Publication status | Published - Jan 1 2014 |
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All Science Journal Classification (ASJC) codes
- Agronomy and Crop Science
- Forestry
- Renewable Energy, Sustainability and the Environment
- Waste Management and Disposal
Cite this
A mechanistic study on the reaction pathways leading to benzene and naphthalene in cellulose vapor phase cracking. / Norinaga, Koyo; Yang, Huamei; Tanaka, Ryota; Appari, Srinivas; Iwanaga, Keita; Takashima, Yuka; Kudo, Shinji; Shoji, Tetsuya; Jun-Ichiro, Hayashi.
In: Biomass and Bioenergy, Vol. 69, 01.01.2014, p. 144-154.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - A mechanistic study on the reaction pathways leading to benzene and naphthalene in cellulose vapor phase cracking
AU - Norinaga, Koyo
AU - Yang, Huamei
AU - Tanaka, Ryota
AU - Appari, Srinivas
AU - Iwanaga, Keita
AU - Takashima, Yuka
AU - Kudo, Shinji
AU - Shoji, Tetsuya
AU - Jun-Ichiro, Hayashi
PY - 2014/1/1
Y1 - 2014/1/1
N2 - The reaction pathways leading to aromatic hydrocarbons such as benzene and naphthalene in gas-phase reactions of multi-component mixtures derived from cellulose fast pyrolysis were studied both experimentally and numerically. A two-stage tubular reactor was used for evaluating the reaction kinetics of secondary vapor phase cracking of the nascent pyrolysates at temperature ranging from 400 to 900°C, residence time from 0.2 to 4.3s, and at 241kPa. The products of alkyne and diene were identified from the primary pyrolysis of cellulose even at low temperature range 500-600°C. These products include acetylene, propyne, propadiene, vinylacetylene, and cyclopentadiene. Experiments were also numerically validated by a detailed chemical kinetic model consisting of more than 8000 elementary step-like reactions with over 500 chemical species. Acceptable capabilities of the kinetic model in predicting concentration profiles of the products enabled us to assess reaction pathways leading to benzene and naphthalene via the alkyne and diene from primary pyrolysates of cellulose. C3 alkyne and diene are primary precursors of benzene at 650°C, while combination of ethylene and vinylacetylene produces benzene dominantly at 850°C. Cyclopentadiene is a prominent precursor of naphthalene. Combination of acetylene with propyne or allyl radical leads to the formation of cyclopentadiene. Furan and acrolein are likely important alkyne precursors in cellulose pyrolysis at low temperature, whereas dehydrogenations of olefins are major route to alkyne at high temperatures.
AB - The reaction pathways leading to aromatic hydrocarbons such as benzene and naphthalene in gas-phase reactions of multi-component mixtures derived from cellulose fast pyrolysis were studied both experimentally and numerically. A two-stage tubular reactor was used for evaluating the reaction kinetics of secondary vapor phase cracking of the nascent pyrolysates at temperature ranging from 400 to 900°C, residence time from 0.2 to 4.3s, and at 241kPa. The products of alkyne and diene were identified from the primary pyrolysis of cellulose even at low temperature range 500-600°C. These products include acetylene, propyne, propadiene, vinylacetylene, and cyclopentadiene. Experiments were also numerically validated by a detailed chemical kinetic model consisting of more than 8000 elementary step-like reactions with over 500 chemical species. Acceptable capabilities of the kinetic model in predicting concentration profiles of the products enabled us to assess reaction pathways leading to benzene and naphthalene via the alkyne and diene from primary pyrolysates of cellulose. C3 alkyne and diene are primary precursors of benzene at 650°C, while combination of ethylene and vinylacetylene produces benzene dominantly at 850°C. Cyclopentadiene is a prominent precursor of naphthalene. Combination of acetylene with propyne or allyl radical leads to the formation of cyclopentadiene. Furan and acrolein are likely important alkyne precursors in cellulose pyrolysis at low temperature, whereas dehydrogenations of olefins are major route to alkyne at high temperatures.
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UR - http://www.scopus.com/inward/citedby.url?scp=84905246557&partnerID=8YFLogxK
U2 - 10.1016/j.biombioe.2014.07.008
DO - 10.1016/j.biombioe.2014.07.008
M3 - Article
AN - SCOPUS:84905246557
VL - 69
SP - 144
EP - 154
JO - Biomass and Bioenergy
JF - Biomass and Bioenergy
SN - 0961-9534
ER -