Faculty Profiles - NORINAGA Koyo

Regulation of temperature distribution in fixed bed reactor for CO<inf>2</inf> methanation through “CHESS” monolith structure catalyst Reviewed

Zhang W., Lin Y., Zhang Y., Li T., Li J., Chen Z., Norinaga K.

Applied Thermal Engineering Vol. 236 2024.1

Language：English Publishing type：Research paper (scientific journal) Publisher：Applied Thermal Engineering

CO2 methanation suffers from the problem of temperature runaway phenomenon due to its exothermic nature. To mitigate this issue, optimizing catalyst structure becomes crucial. This work established numerical models to investigate the CO2 methanation reaction and heat/mass transfer process in the reactor with porous pellet and monolithic catalysts. Results show that the reactor with porous pellets has the lowest carbon conversion per unit pressure drop due to its large total pressure drop. In contrast, the reactor with monolith exhibits a much larger carbon conversion per unit pressure drop but a smaller absolute carbon conversion. Based on this, an improved “CHESS” monolith structure was proposed and improved, which not only maintains a high absolute carbon conversion (62.6 %) but also enhances the heat transfer process in CO2 methanation. Moreover, compared with the reactor with porous pellets, the maximum temperature in the improved “CHESS” monolith was decreased by around 11.09 %.

DOI： 10.1016/j.applthermaleng.2023.121826

1-02　Tar and soot formation characteristics of various coals in a two-stage entrained flow coal gasifier revealed by detailed chemical kinetic modeling Reviewed

LI Tailin, NAKAMURA Maiki, UEHARA Yusuke, MACHIDA Hiroshi, NORINAGA Koyo

Proceedings of Conference on Coal Science Vol. 60 ( 0 ) page： 4 - 5 2023.10

Language：Japanese Publishing type：Research paper (scientific journal) Publisher：The Japan Institute of Energy

Substituting air with either CO2 or H2O in the gasifying agents presents a viable strategy for promptly integrating a carbon-neutral energy vector into coal gasification technology, concurrently mitigating harmful particulate matter emissions. However, fully understanding the evolution of tar in the practical gasifier has proven to be challenging owing to complex mixture of the scale of reactors. This study presents a detailed kinetic investigation of tar and soot formations from the gas-phase reactions in the reductor of a two-stage entrained flow coal gasifier under oxy-fuel (O2/CO2, O2/H2O) atmospheres. The effects of temperature and coal types were studied. The results show that benzene, followed by naphthalene and phenanthrene, serves as the primary tar products. Higher temperature promotes tar reduction, especially under O2/H2O condition. Moreover, soot yield under the O2/H2O condition is less than that under the O2/CO2 condition owing to weaker hydrogen abstraction acetylene addition route. Soot yield decreases with the temperature rises. This work provides valuable insights and guidance for the reduction of tar and soot in the two-stage entrained flow coal gasifier under oxy-fuel atmospheres.

DOI： 10.20550/jiesekitanronbun.60.0_4

1-08　The computational fluid dynamics analysis resolved at the formed catalyst shape level of CO2 hydrogenation reactor Reviewed

SHIMADA Taiki, LIN Yixiong, NAKAMURA Maki, NORINAGA Koyo

Proceedings of Conference on Coal Science Vol. 60 ( 0 ) page： 16 - 17 2023.10

Language：Japanese Publishing type：Research paper (scientific journal) Publisher：The Japan Institute of Energy

This paper reports a 3D computational fluid dynamics simulation of carbon dioxide (CO2) methanation in a shell-and-tube reactor resolved to the catalyst geometry level. Fluid flow, heat transfer, and mass transfer are calculated, and the local distribution of gas and solid phases in the reactor is shown in detail. To generalize the simulation model, the catalyst effectiveness factor was treated as a variable, and the catalyst effectiveness factor equation and its parameters were investigated. As a result, the catalyst effective coefficient derived from the general Thiele modulus was the best agreement for the present computational model. For higher accuracy, the equations need to be improved to be more suitable for more reality models and chemical reaction equations.

DOI： 10.20550/jiesekitanronbun.60.0_16

CFD simulation of CO2 methanation through the Sabatier reaction in a shell-and-tube reactor incorporating phase change on the shell side Reviewed

Kazui Fukumoto, Wei Zhang, Risa Mizoguchi, Yixiong Lin, Cheolyong Choi, Hiroshi Machida, Koyo Norinaga

Fuel Vol. 349 page： 128126 - 128126 2023.10

Modeling the Chemical Structures of Coals with Different Classifications Using Mean Molecular Weights

Hata Yuki, Hayashizaki Hideyuki, Takanohashi Toshimasa, Takahashi Takafumi, Kanehashi Koji, Norinaga Koyo

Tetsu-to-Hagane Vol. 109 ( 10 ) page： 792 - 801 2023.10

Language：Japanese Publishing type：Research paper (scientific journal) Publisher：The Iron and Steel Institute of Japan

The chemical structure models for the extractions and residues of two types of bituminous coals, A and B, were constructed. The molecular weights of the extractions were determined via gel permeation chromatography (GPC). New standard materials with structures similar to those of coal extraction (i.e., 9, 10- diphenylanthracene, 5,6,11,12-tetraphenylnaphthracene, and chemical compounds A (Mw = 811) and B (Mw = 1135), which were synthesized using the coupling reaction) were adopted for GPC in order to obtain more accurate mean molecular weights than those in literature. Furthermore, a support program for constructing chemical structure models based on 1H nuclear magnetic resonance (NMR) spectra was adopted. The coal models constructed suitably indicate the differences between the types of coal. In particular, it is found that a high pyridine-insoluble fraction extracted rate, which accounts for the most significant difference between the total extracted rates for coals A and B, enhance the coking property of coal A. In addition, the cluster size in the magic solvent-insoluble fraction might affect the softening property of coal.

DOI： 10.2355/tetsutohagane.tetsu-2023-042

Facile Synthesis and Insight of Atomically Dispersed Ni Catalyst on N-Doped Carbonized Lignin for Highly Efficient Electrochemical CO2 Reduction to CO Reviewed

Park, GD; Sirisomboonchai, S; Norinaga, K

CHEMSUSCHEM Vol. 16 ( 16 ) page： e202300530 2023.8

Language：English Publishing type：Research paper (scientific journal) Publisher：ChemSusChem

For the electrochemical CO2 reduction reaction (CO2RR), the single-metal atom catalysts (SACs) on N-doped carbon are considered promising alternatives to conventional catalysts owing to their unique electrocatalytic properties. However, environmentally friendly methods to prepare SACs are still required. Herein, Ni SAC was synthesized using lignin derived from biomass whose structural and chemical properties render it suitable as both a base carbon matrix and a metal chelating agent. The coordination environment of active Ni−Nx sites was readily manipulated by controlling thermal activation. The Ni SAC on lignin-derived N-doped carbon achieved an outstanding CO Faradaic efficiency of 98.2 % at −0.9 V vs. RHE, which is comparable to those of conventional SACs. Experimental results combined with DFT calculations demonstrate the optimal conditions for manufacturing Ni SAC which is highly selective for CO2-to-CO conversion and the effect of the electronic structure of Ni atom on CO2RR kinetics.

DOI： 10.1002/cssc.202300530

6-1-1 Overall electrochemical CO2 reduction - oxygen evolution reaction system via electrodeposition bimetallic covered Cu-foam based electrode Reviewed

SIRISOMBOONCHAI Suchada, MACHIDA Hiroshi, NORINAGA Koyo

Proceedings of the Annual Conference of The Japan Institute of Energy Vol. 32 ( 0 ) page： 116 - 117 2023.8

Language：English Publishing type：Research paper (scientific journal) Publisher：The Japan Institute of Energy

CO2 reduction reaction(CO2RR), as a potential path toward converting CO2 to fuel, is of great significance for alleviating the shortage of fossil fuels and combatting global climate change. Cu foam (CF) exhibits high electrochemical water splitting and CO2 reduction activity. Practical electrochemical overall CO2RR−OER two-electrode systems include a CO2RR at the cathode and an oxygen evolution reaction (OER) at the anode. Herein, we emphasized the CF-modified surface for the two-side reaction by constructing earth-abundant materials on the CF-modified surface with InZnCu/CF as the cathode and Cu(OH)2 NWs@NiCo-LDH as the anode. These were efficient for a CO2RR system with a potential close to an ideal thermodynamic potential for an overall CO2RR−OER. Although this system had different metal composites on both sides, this still allowed a sustainable operation for 40 h with high efficiency. Moreover, we emphasized a further development in scalability. Thus, the energy input for the conversion of CO per ton of CO2 resulted in a low range. The demonstration of the CO2RR−OER provided a facile method of fabricating electrodes based on CF and a constructed overall CO2RR system, which will guide the future development of practical industrial applications.

DOI： 10.20550/jietaikaiyoushi.32.0_116

4-4-1 Effect of fluid temperature on heat transfer and flow behavior in a sublimation tank Reviewed

YAMAGUCHI Hiroyasu, UEHARA Yusuke, MACHIDA Hiroshi, NORINAGA Koyo, SAITO Yasuhiro

Proceedings of the Annual Conference of The Japan Institute of Energy Vol. 32 ( 0 ) page： 90 - 91 2023.8

Language：Japanese Publishing type：Research paper (scientific journal) Publisher：The Japan Institute of Energy

This study investigated the temperature distribution in a laboratory-scale sublimation tank. Numerical simulations in the sublimation tank which cooled CO2 gas at a cold plate were performed to examine the effect of the inlet and initial temperatures of CO2 gas on the temperature distribution. The results showed that the inlet temperature had a minimal impact on the temperature distribution in the tank due to the low flowrate of the gas. In contrast, a decrease in the initial temperature resulted in the increase of the sublimation region below the sublimation temperature, indicating the possibility of dry ice deposition in areas other than near the cold plate.

DOI： 10.20550/jietaikaiyoushi.32.0_90

4-5-1 Design and Optimization of the Flexible Poly-generation Process for Methanol and Formic Acid from CO2 Hydrogenation Under Uncertain Product Prices☆ Reviewed

LI Qiao, MACHIDA Hiroshi, NORINAGA Koyo

Proceedings of the Annual Conference of The Japan Institute of Energy Vol. 32 ( 0 ) page： 98 - 99 2023.8

Language：English Publishing type：Research paper (scientific journal) Publisher：The Japan Institute of Energy

During the design of the carbon capture and hydrogen storage process, a flexible CO2 hydrogenation poly-generation process for methanol and formic acid synthesis was developed to reduce recycling flow and feedstock losses in the single methanol synthesis process and increase product diversity. This poly-generation process is formulated as the MINLP model, which was optimized using a two-stage optimization strategy with the unscented transform tool to obtain optimal design and operating parameters that are computationally tractable. For investment decision-makers, the flexible polygeneration process can achieve higher profits and reduce potential market risks when they have adequate financing.

DOI： 10.20550/jietaikaiyoushi.32.0_98

Insights into structure-performance relationship in radial flow fixed bed reactor for CO<inf>2</inf> methanation Reviewed

Zhang W., Lin Y., Norinaga K.

International Journal of Hydrogen Energy Vol. 48 ( 64 ) page： 24594 - 24606 2023.7

Language：English Publishing type：Research paper (scientific journal) Publisher：International Journal of Hydrogen Energy

The extraction of petroleum and natural gas is often accompanied by a large number of associated gases, especially the high CO2 content reservoirs facing the emission of a large amount of CO2. CO2 methanation is recognized as one of the suitable candidates for CO2 utilization to reduce the emission of CO2. Because of the highly exothermic nature of the reaction, however, it is very important to enhance the heat transfer process inside the reactor and inhibit the formation of hot spots. In the fixed bed reactor, the heat transfer in the radial direction is greatly limited compared with that in the axial direction. Thus, this work adopted the radial flow reactor to evaluate the CO2 methanation process by the means of a numerical model based on OpenFOAM. Four types of radial flow reactor configurations, namely centrifugal Z-type, centrifugal Π-type, centripetal Z-type, and centripetal Π-type, were compared. The fluid flow, heat transfer, and reaction performances for these reactors were discussed under consistent operating conditions. Results show that the centrifugal Π-type structure has the most uniform flow field. In terms of heat transfer and reaction performance, the centripetal Z-type structure is the best among the four radial flow reactor configurations. These findings provide a theoretical basis and technical guidance for designing and developing radial flow reactors.

DOI： 10.1016/j.ijhydene.2023.03.343

Polycyclic aromatic hydrocarbons (PAHs) and soot formations under different gasifying agents: Detailed chemical kinetic analysis of a two-stage entrained flow coal gasifier Reviewed

Tailin Li, Cheolyong Choi, Kazui Fukomoto, Hiroshi Machida, Koyo Norinaga

Fuel Vol. 343 page： 127876 - 127876 2023.7

Facile pyridinization of bio-based furfural into 3-hydroxypyridines over Raney Fe catalyst Reviewed

Ren, DZ; Jiang, XL; Zhang, NH; Duo, J; Norinaga, K; Huo, ZB

BIOMASS CONVERSION AND BIOREFINERY Vol. 13 ( 9 ) page： 8115 - 8121 2023.6

Language：English Publishing type：Research paper (scientific journal) Publisher：Biomass Conversion and Biorefinery

Production of pyridine derivatives from bio-based feedstocks instead of fossil fuels is a promising strategy. The development of effective heterogeneous catalysts and mild reaction systems for pyridinization of renewable biomass derivatives remains a huge challenge. In this article, a direct and environment-friendly method was reported to produce 3-hydroxypyridine from bio-based furfural in water over a Raney Fe catalyst. Raney Fe exhibited an efficient catalytic performance for activation of the aldehyde group of furfural and afforded an 18.2% yield of 3-hydroxypyridine at 120 °C with ammonia as N source. The polymerization of furfural on the catalyst in hot water was the main cause of deactivation, which was verified by the scanning electron microscope (SEM), X-ray diffraction (XRD), and N2 adsorption and desorption analysis. A possible mechanism for this reaction was also proposed. This study provides a new way for academia and industry to realize the synthesis of nitrogen-containing chemicals from biomass and its derivatives.

DOI： 10.1007/s13399-021-01802-5

CFD simulation of CVD reactors in the CH3SiCl3(MTS)/H2 system using a two-step MTS decomposition and one-step SiC growth models Reviewed

Ogawa, T; Fukumoto, K; Machida, H; Norinaga, K

HELIYON Vol. 9 ( 4 ) page： e15061 2023.4

Language：English Publishing type：Research paper (scientific journal) Publisher：Heliyon

In this study, we report on a computational fluid dynamics (CFD) simulation of the chemical vapor deposition reactor of silicon carbide (SiC) in the methyltrichlorosilane (MTS, CH3SiCl3)/H2 system. The formation of SiC thin film is controlled by various process parameters, such as temperature and pressure. In this study, we propose a reaction mechanism of MTS decomposition to SiC growth on a substrate surface for CVD reactors in the CH3SiCl3(MTS)/H2 system. The reaction mechanism has two gas-phase pyrolysis reactions and one SiC film formation reaction. However, we individually build and validate MTS decomposition and SiC growth models to reduce uncertainty. An in-house version of reactingFoam, a reactive flow solver within OpenFOAM v2006, was used as the simulation tool. Our model accurately reproduced MTS decomposition for T = 1100–1350 K and [H2]/[MTS] = 2.65–14 at p = 101,325 Pa. Then, the MTS decomposition model was coupled with the SiC growth model, and the coupled model was applied to the SiC deposition data. The model could reproduce multiple datasets through validation studies.

DOI： 10.1016/j.heliyon.2023.e15061

Lattice Boltzmann study on the effect of hierarchical pore structure on fluid flow and coke formation characteristics in open-cell foam for dry reforming of methane Reviewed

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

CHEMICAL ENGINEERING SCIENCE Vol. 268 2023.3

Language：English Publishing type：Research paper (scientific journal) Publisher：Chemical Engineering Science

Dry reforming of methane (DRM) is one of the feasible strategies for carbon capture and utilization. However, the DRM process has a high tendency toward carbon deposition, which is restricted to industrial applications. In order to further improve coke formation resistance, open-cell foam with hierarchical pore structure was investigated. An artificial algorithm was adopted to construct a hierarchical pore structure in open-cell foam. Based on a 3-D lattice Boltzmann model, this work explored the effect of two hierarchical pore structure parameters on the fluid flow and coke formation characteristics in open-cell foam, which are hierarchical pore volume ratio (V2/V1) and hierarchical pore size ratio (d2/d1). The results indicated that increasing V2/V1 and d2/d1 can significantly promote permeability. Under the restriction ofV2/V1 = 4, from d2/d1 = 1 to 4, the coke formation rate decreases by approximately 57.49 %. These findings provide a theoretical basis and technical guidance for designing and developing open-cell foam reactors.

DOI： 10.1016/j.ces.2022.118380

Estimation of effective thermal conductivity in open-cell foam with hierarchical pore structure using lattice Boltzmann method Reviewed

Japanese Gasification Technology Reviewed

NODA Reiji, ENOMOTO Hiroshi, NAMIOKA Tomoaki, FUSHIMI Chihiro, HOSOKAI Sou, NORINAGA Koyo

Nihon Enerugii Gakkai Kikanshi Enermix Vol. 102 ( 1 ) page： 74 - 79 2023.1

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

APPLIED THERMAL ENGINEERING Vol. 218 2023.1

Language：English Publishing type：Research paper (scientific journal) Publisher：Applied Thermal Engineering

Effective thermal conductivity in open-cell foam with hierarchical pore structure was estimated using lattice Boltzmann method. A new structure algorithm was proposed to reconstruct hierarchical pore structure in open-cell foam. In order to elucidate the heat transfer characteristics in hierarchical pore structure, the effect of structure parameters, namely the hierarchical pore size ratio (d2/d1), the hierarchical pore volume ratio (V2/V1), and temperature on the effective thermal conductivity was investigated. These results indicated that hierarchical pore structure is unfavorable to the effective thermal conductivity in open-cell foam for the heat conduction process. At high temperatures (Tave = 450–1650 K), however, the effective thermal conductivity in hierarchical pore structure is higher than that in uniform pore structure considering heat radiation. Furthermore, for the heat conduction process, a correlation of the effective thermal conductivity related to open-cell foam with hierarchical pore structure was proposed and validated by available experimental data.

DOI： 10.1016/j.applthermaleng.2022.119314

Boosting in-situ hydrodeoxygenation of fatty acids over a fine and oxygen-vacancy-rich NiAl catalyst br Reviewed

Wang, JY; Ren, DZ; Zhang, NH; Lang, JY; Du, YY; He, WH; Norinaga, K; Huo, ZB

RENEWABLE ENERGY Vol. 202 page： 952 - 960 2023.1

Language：English Publishing type：Research paper (scientific journal) Publisher：Renewable Energy

Hydrodeoxygenation (HDO) of fatty acids into long-chain alkanes for aviation fuels with alcohol hydrogen donor at mild condition over Ni-based catalyst is a practicable subject. However, highly active sites design for Ni-based catalyst remains significant challenges. Herein, a fine NiAl particle catalyst with numerous oxygen vacancy sites was fabricated via hydrothermal and reduction treatment. Introduction of small amount of Al species into Ni catalyst not only reduces the Ni particle size exposing plenty of active sites, but also generates oxygen vacancies in AlOx and sets up charge transfer in Ni-AlOx interfaces, thus guarantees the excellent in-situ HDO activity of fatty acids using isopropanol as hydrogen donor. Density functional theory calculation results further reveal that Ni (111) modified by AlOx with oxygen vacancy improves the charge density in Ni-AlOx interface and enhances the adsorption of fatty acid, facilitating the hydrodeoxygenation process. Benefiting from these attributes, Ni–Al0.33Ox presented superior catalytic activity and stability, which achieved 93.2% yield of n-heptadecane at 250 °C and was able to reuse at least 4 times. Therefore, the as-prepared Ni–Al0.33Ox is a promising Ni-based catalyst for alkanes production via in-situ HDO of fatty acids at mild conditions.

DOI： 10.1016/j.renene.2022.11.095

Modeling and estimating kinetic parameters for CO<inf>2</inf> methanation from fixed bed reactor experiments Reviewed

Tsuboi T., Yasuda S., Choi C., Zhang W., Machida H., Norinaga K., Yajima T., Kawajiri Y.

Journal of Advanced Manufacturing and Processing Vol. 5 ( 1 ) 2023.1

Language：English Publishing type：Research paper (scientific journal) Publisher：Journal of Advanced Manufacturing and Processing

CO2 methanation, which converts CO2 and hydrogen into methane as fuel, is one of the promising candidates for the development of CO2 utilization technologies. Recently, a highly active catalyst made of Ni/ZrO2 for methanation has been developed, and is currently investigated as a potential use in a high-performance reactor. However, design of reactor must be carried out carefully, since this reaction is highly exothermic, which may cause reactor runaway and deterioration of catalysts. For this problem, a mathematical model that can predict the behavior inside the reactor is necessary. In this work, we consider the methanation reaction of CO2 in a reactor model and estimate the kinetic parameters in the reaction rate model from experimental data. In the parameter estimation using literature values and Tikhonov regularization, eight kinetic parameters in the rate equations were identified from 64 data points with a wide range of conditions. We confirm that molar fractions at the reactor exit predicted by this reactor model are in good agreement with the experimental results. Furthermore, the developed model was validated to predict the compositions and temperature that were not used in the estimation. We expect the developed model will be a powerful tool for the reactor design.

DOI： 10.1002/amp2.10145

New Data Processing Method for Heavy Oil Components Analyzed by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry Reviewed

KATANO Keita, SUZUKI Teruo, MATSUMOTO Kotaro, KATO Hiroshi, NORINAGA Koyo

Journal of the Japan Petroleum Institute Vol. 66 ( 4 ) page： 101 - 108 2023

Language：Japanese Publishing type：Research paper (scientific journal) Publisher：The Japan Petroleum Institute

A data processing method to automatically assign molecular formulae and correct the abundances was developed and used to improve the reliability and quantitative accuracy of data obtained via Fourier transform ion cyclotron resonance mass spectrometry. The technique was utilized to analyze fractions of atmospheric residue, and assigned molecular formulae for each fraction. The algorithm automatically identified nearly 20,000 heavy oil components. The reliability of the data processing technique was demonstrated by absolute mean mass errors in the range of 0.15-0.23 ppm. Distillation simulation was used to correct the abundances of assigned molecular formulae. The distillation properties were estimated from the molecular formulae, and corrections made to match the simulated results within 1 wt%. The correction factor indicated that lower boiling point components tended to require higher correction factors, suggesting that the ion transport efficiency of the instrument becomes lower in the lower molecular weight region.

DOI： 10.1627/jpi.66.101