研究者詳細 - 則永　行庸

論文 - 則永　行庸

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The effects of nitrogen functional groups and narrow micropore sizes on CO2 adsorption onto N-doped biomass-based porous carbon under different pressure 査読有り

Luo, JY; Liu, BG; Shi, R; Guo, Y; Feng, QG; Liu, Z; Li, LQ; Norinaga, K

MICROPOROUS AND MESOPOROUS MATERIALS 327 巻 2021年11月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Microporous and Mesoporous Materials

The biomass-derived N-doped porous carbons have been proved promising adsorbent material, due to their good CO2/N2 selectivity and excellent CO2 adsorption performance. However, many researchers simply studied the effect of nitrogen groups or narrow micropores (less than 0.7 nm) on CO2 uptake at 1 bar and ignored the role of different pressures. In this study, a promising porous carbon derived from eucalyptus bark with high CO2 adsorption capacity was prepared by urea-assisted hydrothermal and KOH activation. The obtained porous carbons were found to be mainly microporous and showed rich nitrogen content. Among the materials, at 1 bar, NPC700 exhibits high CO2 adsorption of 4.20 mmol/g and 6.98 mmol/g at 25 °C and 0 °C, respectively. Based on Grand canonical Monte Carlo (GCMC) simulation, the adsorption density and adsorption energy on graphite slit pore with different pore sizes (0.6–2.0 nm) and N-doped functional groups (pyridinic-N, pyrrole-N and graphitic-N) were calculated. And the results showed that the nitrogen functional groups played a crucial contribution on CO2 adsorption capacity at relative low pressure (0–0.16 bar). In the case of relative high pressure (0.16–1 bar), the narrow micropores volume determined the CO2 uptake capacity.

DOI： 10.1016/j.micromeso.2021.111404

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Inhibition of temperature runaway phenomenon in the Sabatier process using bed dilution structure: LBM-DEM simulation 査読有り

Lin, YX; Yang, C; Choi, C; Zhang, W; Fukumoto, K; Machida, H; Norinaga, K

AICHE JOURNAL 67 巻 ( 10 ) 2021年10月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：AIChE Journal

The Sabatier process is promising for carbon dioxide utilization and energy storage. However, the serious problem that limits more comprehensive industrial applications is catalyst deactivation due to the temperature runaway phenomenon. The inert particle dilution approach, including the mixing dilution method and layered dilution method is applied to solve this problem. Based on the lattice kinetic scheme-lattice Boltzmann method (LKS-LBM), the effects of three parameters in bed dilution structure reconstructed by the discrete element method (DEM) on temperature distribution and carbon conversion rate were discussed, so as to investigate the relationship between packing structure and temperature distribution. Furthermore, numerical results indicated that an optimal bed dilution structure, which not only can control the peak temperature below the critical temperature to avoid coking and sintering of catalyst, but also can improve the conversion rate by almost 18% compared with the structure without dilution under the same circumstance.

DOI： 10.1002/aic.17304

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Comprehensive Compositional Analysis of Heavy Oil Using Fourier Transform Ion Cyclotron Resonance Mass Spectrometry and a New Data Analysis Protocol 査読有り

Katano, K; Teratani, S; Suzuki, T; Tanaka, R; Kato, H; Norinaga, K

ENERGY & FUELS 35 巻 ( 17 ) 頁： 13687 - 13699 2021年9月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Energy and Fuels

A sequential method that deterministically estimates the molecular composition of heavy oil is reported. A sample of vacuum residua is preseparated into seven fractions: saturated (Sa), aromatic fractions containing one, two, and three or more rings (1A, 2A, and 3A+, respectively), polar and polyaromatic (Po and PA, respectively) resins, and asphaltene (As). The analysis by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) uses one of three different ionization methods depending on the type of structure. Paraffinic species in Sa are ionized by Ag cationization and laser desorption. Aromatic species in 1A, 2A, 3A+, and Po are ionized by atmospheric pressure photoionization. Poorly volatile and condensed aromatic species in PA and As are ionized by laser desorption ionization. Collision-induced dissociation (CID) is used by the FT-ICR MS instrument to determine the structural building blocks. A new data analysis protocol developed to represent petroleum molecules named the composition and structure analyzer (CSA) requires data obtained before and after CID as inputs. The CSA provides juxtaposed attributes for chemical-structure description (JACDs). Structural information based on JACDs can be used to predict physical and chemical properties such as boiling and melting points and solubility parameters and build attribute-based reaction models, to optimize heavy oil upgrading processes.

DOI： 10.1021/acs.energyfuels.1c01429

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Density and Viscosity Calculation of a Quaternary System of Amine Absorbents before and after Carbon Dioxide Absorption 査読有り

Tran, KVB; Sato, M; Yanase, K; Yamaguchi, T; Machida, H; Norinaga, K

JOURNAL OF CHEMICAL AND ENGINEERING DATA 66 巻 ( 8 ) 頁： 3057 - 3071 2021年8月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Journal of Chemical and Engineering Data

Viscosity and density of amine absorbents affect directly their flow, which is involved in the process design and simulation of carbon dioxide capture. A mixture of 2-(ethyl amino) ethanol (EAE), diethylene glycol diethyl ether (DEGDEE), and water changes its phase from homogeneous to two-liquid ones on CO2 absorption. It is difficult to calculate the viscosity and density of this phase separation solution, especially those of quaternary-component phases. In this research, models to calculate the density and viscosity of the quaternary-component system of EAE/DEGDEE/water/carbamate were suggested based on nonrandom two-liquid (NRTL)-DVOL and NRTL-DVIS models. Given the component concentrations, these models can replicate well the viscosity and density of the solutions. A good calculation result with a few numbers of parameters makes the models simple and easy to use.

DOI： 10.1021/acs.jced.1c00195

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Production of light hydrocarbons from organosolv lignin through catalytic hydrogenation and subsequent fast pyrolysis 査読有り

Zhang, LJ; Choi, C; Machida, H; Norinaga, K

JOURNAL OF ANALYTICAL AND APPLIED PYROLYSIS 156 巻 2021年6月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Journal of Analytical and Applied Pyrolysis

Valorization and utilization of lignin have been drawing increasing attention recently. Hydroprocess is one of the main technologies, which can reduce organic compounds and partially depolymerize the macromolecular structure of lignin. The mechanism of lignin hydroprocess has been extensively discussed focusing on hydrogenolysis. In contrast, the solid residue regarded as unreacted or depolymerized lignin has drawn less attention so far. This study proposes an integrated process that consists of catalytic hydrogenation and subsequent fast pyrolysis for valorizing lignin. The results showed that 48−87 wt.% of solid product could be recovered as hydrogenated lignin (H-EOL) after hydrogenation at 200–250 ℃ for 1−7 h. Chemical structure of H-EOL was comprehensively investigated by means of elemental analysis, FTIR, 13C & 1H NMR, and TGA. Furthermore, behavior of fast pyrolysis of H-EOL was detected here for the first time. H-EOL has higher hydrogen to carbon atomic effective ratio(H/Ceff ratio) and achieves the increasing reactivity of thermal decomposition. H-EOL yields light olefins double as much as raw ethanol organosolv lignin (EOL). And the formation of alkanes (C1-C4), benzene, and toluene was promoted to various degrees, while the yield of carbon monoxide, carbon dioxide, and vapor decreased. A novel and efficient pretreatment method has been provided to valorize lignin, which is instructive for subsequent research.

DOI： 10.1016/j.jaap.2021.105096

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An Approach to Simulate Vapor Phase Reactions of Coal Volatiles in a Reducing Section of the Two Stage Entrained Flow Gasifier with a Detailed Chemical Kinetic Model

Choi, C; Adachi, N; Zhang, W; Machida, H; Hayashi, J; Watanabe, H; Norinaga, K

JOURNAL OF CHEMICAL ENGINEERING OF JAPAN 54 巻 ( 6 ) 頁： 334 - 343 2021年6月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Journal of Chemical Engineering of Japan

An approach in predicting reactions undergone by coal volatiles in a reducing section (reductor) of an air-blown two-stage entrained flow gasifier toward designing a better gasification process was proposed. A detailed chemical kinetic model was applied to simulate chemical reactions of a complex molecular mixture of the coal volatiles evolved due to rapid pyrolysis of coal fed into the reductor. The composition of volatiles was determined based on pyrolysis-gas chromatography experiments, where 22 compounds, including inorganic gases (H2, H2O, CO and CO2), light hydrocarbon gases (C1–C4), and aromatic hydrocarbons (benzene to pyrene) were identified. Gas composition at the reductor inlet was estimated by integrating the information on the experimentally obtained molecular composition of the volatiles, and the thermodynamically calculated composition of inorganic gases generated from the combustor and the coal feeding rates into reductor and combustor. Concentration profiles of the individual chemical species, as well as soot particles together with the flow direction of the reductor, were revealed using an extended detailed chemical kinetic model involving 202 species, 1351 gas-phase reactions, and 101 surface reactions for soot formation and growth. The simulation revealed that near-complete decomposition of tar regarded as a set of all aromatic hydrocarbons is likely to require operation temperature of the reductor at temperatures as high as 1200°C, when the combustor is operated at 1800°C.

DOI： 10.1252/jcej.20we171

A Review on Detailed Kinetic Modeling and Computational Fluid Dynamics of Thermochemical Processes of Solid Fuels 査読有り

Choi, C; Zhang, W; Fukumoto, K; Machida, H; Norinaga, K

ENERGY & FUELS 35 巻 ( 7 ) 頁： 5479 - 5494 2021年4月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Energy and Fuels

This review presents the recent advances in computational approaches to understand thermochemical reactions of solid fuels with minimized empirical factors. It includes studies on kinetic modeling of gas-phase reactions of multicomponent molecular mixtures of volatiles derived from primary pyrolysis of solid fuels using a database for elementary reactions. Mechanistic studies to model the devolatilization of biomass and coal upon heating are also mentioned. The efforts to integrate the kinetic model with computational fluid dynamics to understand the flow and heat transfer behavior of industrial reactors for solid fuel conversions, including gasification and combustion, are reviewed. These advances are primarily based on the conventional forward analysis that provides a deeper understanding of chemically reacting flows of fuels undergoing thermochemical reactions. For the further development of the thermochemical conversion technology, it can be expected to develop alternative approaches such as inverse analysis to determine the optimal reactor design and operating conditions.

DOI： 10.1021/acs.energyfuels.0c04052

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Catalytic hydrotreatment of alkaline lignin and its consequent influences on fast pyrolysis 査読有り

Zhang, LJ; Choi, C; Machida, H; Huo, ZB; Norinaga, K

CARBON RESOURCES CONVERSION 4 巻頁： 219 - 229 2021年

担当区分：最終著者,　責任著者記述言語：日本語掲載種別：研究論文（学術雑誌）出版者・発行元：Carbon Resources Conversion

The current state of lignin has been characterized by these three: (1) as one of the main components in lignocellulosic biomass with an abundant amount; (2) not be taken seriously but treated as a waste product; (3) underutilized due to a complex and stubborn structure. However, lignin can be a rich source for hydrocarbons and aromatic compounds when gives appropriate utilization. In this work, we have studied the hydrotreatment of alkaline lignin (AL) under relatively mild conditions and further investigated the characterization of hydrogenated lignin (HL), especially the behavior during fast pyrolysis. The recovery of the HL decreased with increasing reaction temperature from 60 wt.% to 41 wt.% in the range of 150–250 ℃. The hydrotreated products were analyzed using Elemental Analysis, FTIR (for HL) and GC–MS (for bio-oil). The HL samples were found to have a higher hydrogen/carbon atomic effective ratio (H/Ceff ratio) and a higher degree of saturation than AL. Compared to the internal structure of the lignin before and after hydrotreatment, the side chain groups were removed from AL during the process. After that, from the fast pyrolysis of HL, it was observed that more light hydrocarbons and aromatic compounds were formed than that of AL. Furthermore, fast pyrolysis in the hydrogen atmosphere revealed that more volatile fractions were released compared to the Helium atmosphere. The total olefins yield was increased for HL compared AL from 1.02 wt.% to 3.1 wt.% at 250 ℃ for 7 hours. This study of HL is instructive to some extent for the industrial utilization of lignin.

DOI： 10.1016/j.crcon.2021.09.001

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A comprehensive study on butanolysis of furfuryl alcohol to butyl levulinate using tungstated zirconia and sulfonated carbon catalysts 査読有り

Thuppati, UR; Choi, C; Machida, H; Norinaga, K

CARBON RESOURCES CONVERSION 4 巻頁： 111 - 121 2021年

担当区分：最終著者,　責任著者記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Carbon Resources Conversion

This work presents the formation of butyl levulinate, a potential fuel additive, and an excellent renewable chemical obtained by the butanolysis of furfuryl alcohol (FAL) over a solid acid catalyst. The butanolysis of furfuryl alcohol reaction is a strong function of acidity for which tungstated zirconia (WO3-ZrO2), a robust solid acid catalyst, and a sulfonated carbon catalyst were employed to produce high yields of butyl levulinate targeting a lower initial molar ratio of butanol to FAL. A maximum of 28 mol% yield of butyl levulinate was obtained with tungstated zirconia catalyst. Easily prepared sulfonated carbon catalyst at high reaction temperatures facilitated the complete conversion of reaction intermediate, 2-butoxymethylfuran (2-BMF) through which butyl levulinate was formed, and as high as 80 mol% of butyl levulinate yield was produced at an initial mole ratio of 8.5:1 of butanol to FAL. The better results of sulfonated carbon catalyst could be attributed to the presence of -SO3H, carboxylic acid, and phenolic OH groups on the carbon surface.

DOI： 10.1016/j.crcon.2021.03.003

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Durability and fire-hazardous-risk evaluation of unique phase separation solvent using high-boiling amine and ether 査読有り

Maeda N., Kishimoto A., Machida H., Yamaguchi T., Yanase K., Norinaga K.

15th Greenhouse Gas Control Technologies Conference 2021, GHGT 2021 2021年

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：15th Greenhouse Gas Control Technologies Conference 2021, GHGT 2021

Durability and fire hazard risk evaluation were conducted to determine the process feasibility on the unique phase separation solvent with low regeneration temperature (90 °C), consisting of amine, ether, and small amount of water. The results we obtained are as follows; I) The amine degradation rate of the phase separation solvent would be less than 1/10 of that of monoethanolamine (MEA), which was contributed by its high oxidative resistant nature and low regeneration temperature. II) The gas composition formed in the absorber was completely out of combustible range and almost no accumulations of explosive compounds such as peroxides were observed when in contact with 6 % oxygen containing gas (dry base). Therefore, we believe that the phase separation solvent is applicable to the treatment of exhaust gas from coal-fired thermal power plants.

Scopus

Energy analysis of CO<inf>2</inf> separation process with low energy consumption using phase separation solvent 査読有り

Maeda N., Nakanishi K., Kishimoto A., Machida H., Yamaguchi T., Norinaga K.

15th Greenhouse Gas Control Technologies Conference 2021, GHGT 2021 2021年

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：15th Greenhouse Gas Control Technologies Conference 2021, GHGT 2021

We calculated the energy required for regeneration when the phase separation solvent solvent is applied to the treatment of exhaust gas from coal-fired power plants. This solvent is characterized by regeneration at a low temperature of less than 100°C. As a result, it was clarified that under ideal conditions with no pressure drop and no heat loss, the required energy could be suppressed to 1.5 GJ/ton-CO2 by satisfying the following conditions; i) pinch point of the heat exchanger between rich-amine and lean-amine: 1 °C, ii) water concentration of the solvent: kept at 10 wt%, iii) COP of the heat pump: 5.5. However, increase of the pinch point, increase of the water concentration, and decrease of the COP will all result in a significant increase in the required energy. Therefore, in order to realize a process with low energy consumption, it is essential to meet these design constraints.

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2-14 触媒層温度及びガス組成分布を考慮した解析によるメタネーション反応速度モデルの検討査読有り

安田将也, 町田洋, 則永行庸

石炭科学会議発表論文集 57 巻 ( 0 ) 頁： 44 - 45 2020年10月

2-16 CO2分離回収の省エネルギー化に向けた相分離吸収剤およびH2ストリッピングプロセスの開発査読有り

町田洋, 走出龍星, 鈴木健弘, 西尾仁志, 柳瀬慶一, チャンクウィン, 則永行庸

石炭科学会議発表論文集 57 巻 ( 0 ) 頁： 48 - 49 2020年10月

Online composition analysis of phase separation solvent for carbon dioxide capture using ATR-FT-IR 査読有り

Sato M., Tran K.V.B., Yamaguchi T., Machida H., Norinaga K.

Journal of Advanced Manufacturing and Processing 2 巻 ( 4 ) 2020年10月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Journal of Advanced Manufacturing and Processing

An amine solvent that undergoes phase change after absorption of CO2 has been studied to reduce the energy consumed during the CO2 capture process. Depending on the components of the solvent, the CO2-rich phase can be separated for the regeneration step or the component in CO2-lean phase accelerates the regeneration step in the solvent that undergoes liquid-liquid phase change. Since the homogeneous solvent separates into two liquid phases after CO2 absorption, an analysis method to track the change in chemical species during the absorption process, especially at the phase separation time, is necessary to illuminate the phenomenon. To establish an online method to analyze the components of the solvent, a Fourier-transform infrared (FT-IR) spectrometer equipped with an attenuated total reflection (ATR) probe was used during the CO2 absorption of phase separation solvent composed of amine, ether, and water. The calibration samples of amines, ethers, and CO2-loaded solutions were used to develop the partial least square regression model. The consumption of reactants, as well as the formation of products, can be monitored quantitatively using the FT-IR spectra. Utilizing this information, the changes in the chemical species shed light on the phase separation mechanism of this solvent: ether was pushed out of the solvent to form a CO2-lean phase due to its hydrophobicity, while CO2 and its products along with amine and water remain in the CO2-rich phase. Without sampling, this rapid and high-accuracy method is suitable for closed processes, especially for a high-pressure process.

DOI： 10.1002/amp2.10067

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Rate of CO<inf>2</inf> absorption of a phase-separation absorbent 査読有り

Esaki T., Machida H., Norinaga K.

Journal of Advanced Manufacturing and Processing 2 巻 ( 1 ) 2020年1月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Journal of Advanced Manufacturing and Processing

In this study, we evaluated the CO2 absorption characteristics of a phase-separation amine absorbent. The phase-separation absorbent consists of a 30:60:10 (by weight percent) mixture of 2-(ethylamino)ethanol, diethylene glycol diethyl ether, and water. The CO2 absorption rate of the phase-separation absorbent was measured in a lab-scale counter flow absorber. In addition, the CO2 transport phenomena in the absorber were analyzed by performing model fitting. The experimental results revealed that the CO2 absorption rates are different before and after phase separation. In fact, the overall CO2 absorption capacity coefficient after phase separation is 4.5 times higher than that obtained before phase separation. By changing the gas-liquid ratio, we obtained a CO2 recovery ratio of over 80% using the model. Thus, the absorption temperature, CO2 loading, and gas-liquid ratio can be tuned to obtain the desired CO2 recovery ratio.

DOI： 10.1002/amp2.10033

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1-12 CO2メタネーション反応器における伝熱と流動に関する数値解析査読有り

溝口莉彩, 町田洋, 則永行庸

石炭科学会議発表論文集 56 巻 ( 0 ) 頁： 24 - 25 2019年10月

2-5 詳細反応化学速度モデルを用いた噴流床石炭ガス化炉における芳香族炭化水素の改質およびスス生成シミュレーション査読有り

安達希美, 町田洋, 則永行庸

石炭科学会議発表論文集 56 巻 ( 0 ) 頁： 56 - 57 2019年10月

1-22 石炭熱分解時の芳香族クラスター成長により発生する水素の転換反応機構査読有り

福岡鉄也, 町田洋, 則永行庸

石炭科学会議発表論文集 56 巻 ( 0 ) 頁： 44 - 45 2019年10月

1-13 相分離型省エネルギーCO2吸収剤のCO2吸収再生性能評価査読有り

鈴木健弘, 西尾仁志, 柳瀬慶一, 町田洋, 則永行庸

石炭科学会議発表論文集 56 巻 ( 0 ) 頁： 26 - 27 2019年10月

1-2-2 石炭ガス化炉内硫黄化合物転換特性の詳細化学反応速度モデルに基づく解析査読有り

安達希美, 町田洋, 則永行庸

日本エネルギー学会大会講演要旨集 28 巻 ( 0 ) 頁： 10 - 11 2019年7月

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