Detailed chemical kinetic modeling as an innovative approach for understanding complex reactions included in thermochemical conversions of carbon resources

• Project/Area Number: 23686112
• Research Category: Grant-in-Aid for Young Scientists (A)
• Allocation Type: Single-year Grants
• Research Field: Reaction engineering/Process system
• Research Institution: Kyushu University
• Principal Investigator: NORINAGA Koyo 九州大学, 先導物質化学研究所, 准教授 (00312679)
• Co-Investigator(Renkei-kenkyūsha): HAYASHI Jun-ichiro 九州大学, 先導物質化学研究所, 教授 (60218576) ; KUDO Shinji 九州大学, 先導物質化学研究所, 助教 (70588889)
• Project Period (FY): 2011-04-01 – 2014-03-31
• Project Status: Completed (Fiscal Year 2013)
• Budget Amount: ¥16,510,000 (Direct Cost: ¥12,700,000、Indirect Cost: ¥3,810,000); Fiscal Year 2013: ¥3,380,000 (Direct Cost: ¥2,600,000、Indirect Cost: ¥780,000); Fiscal Year 2012: ¥6,760,000 (Direct Cost: ¥5,200,000、Indirect Cost: ¥1,560,000); Fiscal Year 2011: ¥6,370,000 (Direct Cost: ¥4,900,000、Indirect Cost: ¥1,470,000)
• Keywords: 炭素資源 / 熱化学転換 / ガス化 / 熱分解 / 反応速度モデル / 素反応 / 詳細化学 / バイオマス / 石炭 / 反応機構 / 反応速度論 / シミュレーション / 分析 / エネルギー / 素反応モデル / 質量分析

Research Abstract

The reaction chemistries included in the thermochemical conversion of carbon resources such as cellulose were studied. A two-stage tubular reactor was used for evaluating the reaction kinetics of secondary vapor phase reactions of the nascent pyrolysates. 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 low temperature, while combination of ethylene and vinylacetylene produces benzene dominantly at high temperature. Cyclopentadiene is a prominent precursor of naphthalene. Combination of acetylene with propyne or allyl radical leads to the formation of cyclopentadiene.

Research Products

• [Journal Article] Extended Detailed Chemical Kinetic Model for Benzene Pyrolysis with New Reaction Pathways Including Oligomer Formation (2014)
  • Author(s): Akihiro Kousoku, Koyo Norinaga, and Kouichi Miura
  • Journal Title: Ind. Eng. Chem. Res Volume: 53 (19) Issue: 19 Pages: 7956-7964
  • DOI: 10.1021/ie4044218
  • Peer Reviewed
• [Journal Article] 炭素資源熱化学反応の理解と予測． (2014)
  • Author(s): 則永行庸
  • Journal Title: 炭素資源国際教育研究センターNewsletter Volume: 11 Pages: 2-3
• [Journal Article] バイオマス熱化学反応の理解と予測 (2013)
  • Author(s): 則永行庸
  • Journal Title: 化学工学 Volume: Vol.77(9) Pages: 646-649
  • NAID: 10031193141
  • Peer Reviewed
• [Journal Article] Detailed chemical kinetic modelling of vapour-phase cracking of multi-component molecular mixtures derived from the fast pyrolysis of cellulose (2013)
  • Author(s): Koyo Norinaga, Tetsuya Shoji, Shinji Kudo, Jun-ichiro Hayashi
  • Journal Title: Fuel Volume: 103 Pages: 141-150
  • DOI: 10.1016/j.fuel.2011.07.045
  • Peer Reviewed
• [Journal Article] Rapid pyrolysis of brown coal in a drop-tube reactor with co-feeding of char as a promoter of in situ tar reforming (2013)
  • Author(s): Li-xin Zhang, Toru Matsuhara, Shinji Kudo, Jun-ichiro Hayashi, Koyo Norinaga.
  • Journal Title: Fuel Volume: 112 Pages: 681-686
  • DOI: 10.1016/j.fuel.2011.12.030
  • Peer Reviewed
• [Journal Article] Conversion Characteristics of Aromatic Hydrocarbons in Simulated Gaseous Atmospheres in Reducing Section of Two-Stage Entrained-Flow Coal Gasifier in Air- and 02/C02- (2013)
  • Author(s): Yasuhiro SAKURAI, et al.
  • Journal Title: Energy and Fuels Volume: (掲載確定) Issue: 4 Pages: 1974-1981
  • DOI: 10.1021/ef301658d
  • Peer Reviewed
• [Journal Article] Promoting gas production by controlling the interaction of volatiles with char during coal gasification in a circulating fluidized bed gasification reactor. (2013)
  • Author(s): Koichi Matsuoka, Sou Hosokai, Yoshishige Kato, Koji Kuramoto, Yoshizo Suzuki, Koyo Norinaga, and Jun-ichiro Hayashi
  • Journal Title: Fuel Processing Technology Volume: 116 Pages: 308-316
  • DOI: 10.1016/j.fuproc.2013.07.017
  • Peer Reviewed
• [Journal Article] バイオマス熱化学反応の理解と予測． (2013)
  • Author(s): 則永行庸
  • Journal Title: 化学工学 Volume: 77 Pages: 646-649
  • NAID: 10031193141
• [Journal Article] Catalytic effects of Na and Ca from inexpensive materials on in-situ steam gasification of char from rapid pyrolysis of low rank coal in a drop-tube reactor. (2013)
  • Author(s): Li-xin Zhang, Toru Matsuhara, Shinji Kudo, Naoto Tsubouchi, Jun-ichiro Hayashi, Yasuo Ohtsuka and Koyo Norinaga
  • Journal Title: Fuel Processing Technologｙ Volume: 104 Pages: 1-7
  • DOI: 10.1016/j.fuproc.2013.03.009
  • Peer Reviewed
• [Journal Article] Process Development toward Efficient Charcoal Production from Biomass using Moving Bed Pyrolyzer (2013)
  • Author(s): Yong Huang, Koyo Norinaga, Shinji Kudo, Jun-ichiro Hayashi, Keiji Tomura, Satoshi Horiuchi, Nubuo Takasu
  • Journal Title: Journal of the Society of Powder Technology, Japan Volume: 50 Pages: 173-181
  • NAID: 10031157212
  • Peer Reviewed
• [Journal Article] 素反応解析技術を用いたバイオマス由来ガス組成推算技術の開発 (2012)
  • Author(s): 宮地健、片桐学、藤田理人、神田伸靖、則永行庸
  • Journal Title: 三井造船技報 Volume: 第206号(平成24年07月発行) Pages: 19-24
  • URL: http://www.mes.co.jp/mes_technology/research/pdf/206_04.pdf
• [Journal Article] Catalytic Hydrothermal Reforming of Water-soluble Organics from the Pyrolysis of Biomass Using Ni/carbon Catalyst Impregnated with Pt (2012)
  • Author(s): Saruul Idesh, Shinji Kudo, Koyo Norinaga, and Jun-ichiro Hayashi
  • Journal Title: Energy Fuels Volume: 26 Issue: 1 Pages: 67-74
  • DOI: 10.1021/ef201177b
  • Peer Reviewed
• [Journal Article] Numerical Simulation of Thermal Conversion of Aromatic Hydrocarbons in the Presence of Hydrogen and Steam using a Detailed Chemical Kinetic Model (2011)
  • Author(s): Koyo Norinaga, Ryota Sato, and Jun-ichiro Hayashi
  • Journal Title: Chemical Engineering Journal Volume: 178(15) Pages: 282-290
  • DOI: 10.1016/j.cej.2011.10.003
• [Journal Article] 詳細な化学を考慮した固体燃料熱分解ガスの気相反応速度モデリング (2011)
  • Author(s): 則永行庸, ら
  • Journal Title: 日本エネルギー学会誌 Volume: 90 Pages: 107-113
  • NAID: 110008662185
  • Peer Reviewed
• [Journal Article] 石炭基礎講座(9)熱分解の実験手法と反応特性の理解 (2011)
  • Author(s): 林潤一郎、則永行庸
  • Journal Title: 日本エネルギー学会誌 Volume: 90 Pages: 905-910
  • Peer Reviewed
• [Presentation] Chemical structures and primary pyrolysis characteristics of lignins obtained from different preparation methods (2014)
  • Author(s): Huamei Yang, Kudo Shinji, Hayashi Jun-ichiro, Koyo Norinaga
  • Organizer: 1st Asian Conference on Biomass Science
  • Place of Presentation: Kochi, Japan
  • Year and Date: 2014-01-14
• [Presentation] 固体炭素資源熱化学転換反応の理解と予測 (2013)
  • Author(s): 則永行庸
  • Organizer: 日本エネルギー学会リサイクル部会・ガス化部会勉強会
  • Place of Presentation: 早稲田大学・東京
  • Year and Date: 2013-12-20
• [Presentation] A CFD Study of Non-Catalytic Partial Oxidation of Coke Oven Gas with Considering Turbulence-Chemistry Interaction (2013)
  • Author(s): Ryota Tanaka, Kudo Shinji, Hayashi Jun-ichiro, Watanabe, Koyo Norinaga
  • Organizer: The 26th International Symposium on Chemical Engineering
  • Place of Presentation: Pusan, South Korea
  • Year and Date: 2013-12-07
• [Presentation] Real Time Monitoring of Tarry Component Included in Product Gas from Coal Gasification with Li+ Attachment Ionization Mass Spectrometry (2013)
  • Author(s): Koyo Norinaga, Keita Iwanaga, Kazuhiro Uemura, Li-Xin Zhang, Kudo Shinji, Hayashi Jun-ichiro, Kenji Furuya
  • Organizer: 第12回日中石炭・C1化学シンポジウム
  • Place of Presentation: Fukuoka, Japan
  • Year and Date: 2013-10-29
• [Presentation] Detailed chemical kinetic modeling toward better understanding of complex reactions of multi-component mixtures derived from carbon resources (2013)
  • Author(s): Koyo Norinaga
  • Organizer: The 63rd Canadian Chemical Engineering Conference (Frontier in Chemical Engineering Lecture Series, Application of Clean Coal Technology)
  • Place of Presentation: Fredericton,New Brunswick, Canada
  • Year and Date: 2013-10-23
• [Presentation] 石炭ガス化で生成するタール構成分子リアルタイム計測へのイオン付着イオン化質量分析法の適用 (2012)
  • Author(s): 岩永圭太,工藤真二,則永行庸,林潤一郎,古屋謙治
  • Organizer: 第49回石炭科学会議
  • Place of Presentation: 釧路
  • Year and Date: 2012-10-24
• [Presentation] 石炭ガス化炉模擬雰囲気における芳香族化合物の転換反応機構 (2012)
  • Author(s): 櫻井靖紘,山本修司,工藤真二,則永行庸,林潤一郎
  • Organizer: 第49回石炭科学会議
  • Place of Presentation: 釧路
  • Year and Date: 2012-10-24
• [Presentation] 炭化水素熱化学反応の詳細化学反応速度モデリング (2012)
  • Author(s): 則永行庸
  • Organizer: 日本学術振興会,石炭利用技術第148委員会第135回研究会
  • Place of Presentation: 秋田
  • Year and Date: 2012-08-02
• [Presentation] A mechanistic study on the aromatic hydrocarbon formation upon vapor phase cracking of cellulose (2012)
  • Author(s): Koyo Norinaga, Yuka Takashima, Keita Iwanaga, Ryota Tanaka, Kudo Shinji, Hayashi Jun-ichiro
  • Organizer: 第28回化学反応討論会
  • Place of Presentation: 福岡
  • Year and Date: 2012-06-07
• [Presentation] バイオマス熱分解ガス気相改質反応予測のための基礎研究 (2012)
  • Author(s): 則永行庸
  • Organizer: 第2回九大&産総研バイオマスセミナー
  • Place of Presentation: 東広島(招待)
  • Year and Date: 2012-03-21
• [Presentation] セルロース気相熱分解反応における芳香族炭化水素の生成機構 (2012)
  • Author(s): 高島由花,今村和史,田中亮太,則永行庸,工藤真二,林潤一郎
  • Organizer: 第7回バイオマス科学会議
  • Place of Presentation: 盛岡
  • Year and Date: 2012-01-19
• [Presentation] Application of ion attachment mass spectroscopy for real time monitoring of tarry component included in producer gas from biomass/coal gasification (2012)
  • Author(s): Keita Iwanaga, Kenji Furuya, Shinji Kudo, Jun-ichiro Hayashi, Koyo Norinaga
  • Organizer: The 25th International Symposium on Chemical Engineering
  • Place of Presentation: Okinawa
• [Presentation] Modeling of Reaction Flow in a Reformer for Non-catalytic Partial Oxidation of Hot Coke Oven Gas (2012)
  • Author(s): K. Norinaga, R. Tanaka, S. Kudo, J. Hayashi, H. Watanabe, V. J. Janardhanan
  • Organizer: 62nd Canadian Chemical Engineering Conference Incorporating the 3rd International Symposium on Gasification and its Applications
  • Place of Presentation: Vancourver, Canada
• [Presentation] O2/CO2ガス化炉内模擬ガス雰囲気における芳香族化合物の転換特性 (2012)
  • Author(s): 山本 修司, 櫻井 靖紘, 工藤 真二, 則永 行庸, 林 潤一郎
  • Organizer: 第21回日本エネルギー学会大会
  • Place of Presentation: 東京
• [Presentation] Detailed Chemical Kinetic Modeling toward Better Understanding of Complex Reactions of Multi-component Gas Mixtures Derived from Carbon Resources (2011)
  • Author(s): Koyo Norinaga
  • Organizer: Seminar at Research Center for Composite Materials (RCCM), Shanghai University (SHU)
  • Place of Presentation: 上海(招待)
  • Year and Date: 2011-10-29
• [Presentation] Prediction of Steam Reforming of the Simulated Coke Oven Gas with a Detailed Chemical Kinetic Model (2011)
  • Author(s): Koyo Norinaga, Ryota Sato, Hayashi Jun-ichiro
  • Organizer: International Conference on Coal Science and Technology 201
  • Place of Presentation: Oviedo, Spain
  • Year and Date: 2011-10-10
• [Presentation] バイオマス熱分解揮発成分の二次気相反応に対する素反応解析の適用 (2011)
  • Author(s): 藤田理人,片桐学,宮地健,杉本富男,則永行庸
  • Organizer: 化学工学会第43回秋季大会
  • Place of Presentation: 名古屋
  • Year and Date: 2011-09-14
• [Presentation] コークス炉ガスの接触部分酸化・水蒸気改質反応機構の解明と迅速水素製造システムの構築 (2011)
  • Author(s): 則永行庸
  • Organizer: 公益財団法人鉄鋼環境基金第2回助成研究成果表彰式受賞記念講演会
  • Place of Presentation: 鉄鋼会館(東京都中央区日本橋茅場町)(招待)
  • Year and Date: 2011-09-12
• [Presentation] 炭化水素熱化学反応のモデリングとシミュレーションその基礎と応用 (2011)
  • Author(s): 則永行庸
  • Organizer: 第2回ペトロリオミクス合同勉強会
  • Place of Presentation: 東京神谷町(招待)
  • Year and Date: 2011-09-08
• [Presentation] セルロース気相熱分解反応における芳香族炭化水素の生成機構 (2011)
  • Author(s): 高島由花, ら
  • Organizer: 第7回バイオマス科学会議
  • Place of Presentation: 岩手
• [Presentation] 管状反応器GC,GC/MS直結型分析装置を用いたバイオマス初期熱分解生成物の化学組成分析 (2011)
  • Author(s): 岩永啓太, ら
  • Organizer: 第7回バイオマス科学会議
  • Place of Presentation: 岩手
• [Presentation] 反応熱と改質炉外壁からの放熱を考慮した石炭乾留ガス部分酸化改質反応の数値解析 (2011)
  • Author(s): 田中亮太, ら
  • Organizer: 第48回石炭科学会議
  • Place of Presentation: 新潟
• [Presentation] Detailed chemical kinetic modeling toward better understanding of complex reactions of multi-component mixtures derived from carbon resources
  • Author(s): Koyo Norinaga
  • Organizer: The 63rd Canadian Chemical Engineering Conference (Frontier in Chemical Engineering Lecture Series, Application of Clean Coal Technology)
  • Place of Presentation: Fredericton, New Brunswick, Canada
  • Invited
• [Presentation] チャーガス化現象理解のための表面化学反応 および粒子近傍ガス流れに関する数値解析的研究
  • Author(s): 則永行庸
  • Organizer: 石炭・炭素資源利用技術第148委員会第142回研究会
  • Place of Presentation: 東京
  • Invited
• [Presentation] Detailed chemical kinetic modeling of complex reactions of multi-component mixtures derived from carbon resources
  • Author(s): Koyo Norinaga
  • Organizer: Seminar at Karlsruhe Institute of Technology (KIT) (Prof Deutschmann group)
  • Place of Presentation: Karlsruhe, Germany
  • Invited
• [Presentation] Detailed chemical kinetic modeling for gas-phase partical oxidation of volatiles derived from rapid pyrolysis of ligno-cellulosic biomass
  • Author(s): Narumon Thimthong, Ryota Tanaka, Kudo Shinji, Hayashi Jun-ichiro, Koyo Norinaga
  • Organizer: 1st Asian Conference on Biomass Science
  • Place of Presentation: Kochi, Japan
• [Presentation] 詳細反応速度モデル簡略化による石炭乾留ガス部分酸化改質炉内の反応性乱流解析
  • Author(s): 田中 亮太, 則永 行庸, 工藤 真二, 林 潤一郎, 渡邊裕章
  • Organizer: 第50回石炭科学会議
  • Place of Presentation: 福岡
• [Presentation] Real Time Monitoring of Tarry Component Included in Product Gas from Coal Gasification with Li+ Attachment Ionization Mass Spectrometry
  • Author(s): Koyo Norinaga, Keita Iwanaga, Kazuhiro Uemura, Li-Xin Zhang, Kudo Shinji, Hayashi Jun-ichiro, KENJI FURUYA
  • Organizer: 第12回日中 石炭・Ｃ１化学シンポジウム
  • Place of Presentation: Fukuoka, Japan
• [Presentation] Quantitative Analysis of Products in Secondary Pyrolysis of Lignin toward Detailed Kinetic Modeling
  • Author(s): Huamei Yang, Kudo Shinji, Hayashi Jun-ichiro, Koyo Norinaga
  • Organizer: 第12回日中 石炭・Ｃ１化学シンポジウム
  • Place of Presentation: Fukuoka, Japan
• [Presentation] 褐炭とチャーを同時供給した時のドロップチューブ反応器におけるタールin-situ改質特性
  • Author(s): 張 立欣, 工藤 真二, 林 潤一郎, 則永 行庸
  • Organizer: 第22回日本エネルギー学会大会
  • Place of Presentation: 東京
• [Presentation] イオン付着質量分析法によるガス化ガス中微量芳香族成分のリアルタイム計測
  • Author(s): 則永 行庸, 岩永 圭太, 上村 和大, Zhang Li-xin, 工藤 真二, 林 潤一郎, 古屋 謙治
  • Organizer: 第22回日本エネルギー学会大会
  • Place of Presentation: 東京
• [Presentation] 炭化水素熱化学反応の詳細化学反応速度モデリング
  • Author(s): 則永行庸
  • Organizer: 日本学術振興会石炭利用技術第148委員会第135回研究会
  • Place of Presentation: 秋田
  • Invited
• [Presentation] Kinetic modeling of hydrocarbon pyrolysis toward developing a better CVI process for C/C composite
  • Author(s): Koyo Norinaga
  • Organizer: Seminar at School of Materials Science and Engineering (Prof Shouyang Zhang Research Group), Northwestern Polytechnical University(NWPU)
  • Place of Presentation: 西安, China
  • Invited
• [Book] 荒牧寿弘編著石炭の科学と技術-未来につなぐエネルギー-日本エネルギー学会編 (2013)
  • Author(s): 林潤一郎,則永行庸,松下洋介
  • Total Pages: 400
  • Publisher: コロナ社
  • URL: http://www.coronasha.co.jp/np/isbn/9784339066296/
• [Book] 石炭の科学と技術- 未来につなぐエネルギー - (2013)
  • Author(s): 荒牧寿弘、則永行庸、松下洋介、林潤一郎 編著
  • Total Pages: 400
  • Publisher: コロナ社
• [Book] 石炭 (2013)
  • Author(s): 林潤一郎、則永行庸、松下洋介、荒巻攻
  • Total Pages: 300
  • Publisher: コロナ社
• [Remarks] 研究室ホームページ
  • URL: http://www.carbonres.com/
• [Remarks] 則永 行庸 ホームページ
  • URL: http://www.cm.kyushu-u.ac.jp/hayashi/kn/norinaga_jap.html
• [Remarks] 九州大学研究者情報(則永 行庸
  • URL: http://hyoka.ofc.kyushu-u.ac.jp/search/details/K003438/
• [Remarks] 研究室グループ ホームページ
  • URL: http://www.carbonres.com/
• [Remarks] 研究成果公表Web Page （則永行庸）
  • URL: http://www.cm.kyushu-u.ac.jp/hayashi/kn/norinaga_jap.html
• [Remarks] 九州大学 研究所情報 （則永行庸）
  • URL: http://hyoka.ofc.kyushu-u.ac.jp/search/details/K003438/
• [Remarks] 先導物質化学研究所HP
  • URL: http://www.cm.kyushu-u.ac.jp/
• [Remarks] 林・則永研究室HP
  • URL: http://www.carbonres.com/
• [Remarks] 則永行庸 HP
  • URL: http://www.cm.kyushu-u.ac.jp/hayashi/kn/norinaga_jap.html
• [Remarks] 研究室HP
  • URL: http://www.carbonres.com/
• [Remarks]
  • URL: http://www.cm.kyushu-u.ac.jp/hayashi/kn/norinaga_jap.html
• [Patent(Industrial Property Rights)] バイオマス炭化方法及びバイオマス炭化装置 (2012)
  • Inventor(s): 戸村啓二、則永行庸ら
  • Industrial Property Rights Holder: 戸村啓二、則永行庸ら
  • Industrial Property Rights Type: 特許
  • Filing Date: 2012-12-21
  • Overseas
• [Patent(Industrial Property Rights)] ガス化装置及びガス化装置の運転方法 (2011)
  • Inventor(s): 宮地 健,則永 行庸, ら
  • Industrial Property Rights Holder: 三井造船,九州大学
  • Industrial Property Rights Type: 特許
  • Industrial Property Number: 2011-145827
  • Filing Date: 2011-06-30
  • Overseas
• [Patent(Industrial Property Rights)] 反応シミュレーション装置及びガス化装置 (2011)
  • Inventor(s): 宮地 健,則永 行庸, ら
  • Industrial Property Rights Holder: 三井造船,九州大学
  • Industrial Property Rights Type: 特許
  • Industrial Property Number: 2011-098085
  • Filing Date: 2011-04-26
  • Overseas
• [Patent(Industrial Property Rights)] ガス化装置及びガス化装置の運転方法 (2011)
  • Inventor(s): 宮地 健,則永 行庸, ら
  • Industrial Property Rights Holder: 三井造船,九州大学
  • Industrial Property Rights Type: 特許
  • Industrial Property Number: 2011-071931
  • Filing Date: 2011-03-29
  • Overseas
• [Patent(Industrial Property Rights)] 反応シミュレーション装置およびガス化装置 (2011)
  • Inventor(s): 則永行庸, ら
  • Industrial Property Rights Holder: 九大、三井造船
  • Industrial Property Number: 2011-098085
  • Filing Date: 2011-04-26
• [Patent(Industrial Property Rights)] ガス化装置およびガス化装置の運転方法 (2011)
  • Inventor(s): 則永行庸, ら
  • Industrial Property Rights Holder: 九大、三井造船
  • Industrial Property Number: 2011-145827
  • Filing Date: 2011-06-30