Faculty Profiles - NORINAGA Koyo

Reducing energy required for CO<inf>2</inf> separation and recovery process by employing phase separation solvents Reviewed

Continuous monitoring of char surface activity toward benzene Reviewed Open Access

Choi C., Shima K., Kudo S., Norinaga K., Gao X., Hayashi J.i.

Carbon Resources Conversion Vol. 2 ( 1 ) page： 43 - 50 2019.4

Language：Japanese Publishing type：Research paper (scientific journal) Publisher：Carbon Resources Conversion

Kinetics of thermal decomposition of benzene on lignite-derived char was investigated at 900 °C by applying a new method to continuously monitor the char surface activity. Benzene vapor was continuously forced to pass through a micro fixed bed of char with residence time as short as 7.6 ms, and then detected continuously by a flame-ionization detector. Results showed the presence of two different types of char surfaces; consumptive Type I surface and non-consumptive (sustainable) Type II surface. Type I surface of a partially CO2-gasified char had an capacity of carbon deposit from benzene over 20 wt%-char and an initial activity (represented by a first-order rate constant) as high as 160 s−1. Both of them decreased with increasing carbon deposit due to consumption of micropores accessible to benzene, and finally became zero leaving Type II surface that had a very stable activity with rate constant of 4 s−1. The chars without gasification had capacities of Type I surfaces smaller by two orders of magnitude than the partially gasified char, while the Type II surfaces had activities similar to that of the partially gasified char. It was found that Type II surface converted benzene into not only carbon deposit but also diaromatics and even greater aromatics. Composition of the greater aromatics was unknown because they were deposited onto the reactor wall immediately after passing through the char bed.

DOI： 10.1016/j.crcon.2018.12.001

Effect of SiO<inf>2</inf> on loss of catalysis of inherent metallic species in CO<inf>2</inf> gasification of coke from lignite Reviewed Open Access

Choi C., Ashik U.P.M., Kudo S., Uebo K., Norinaga K., Hayashi J.i.

Carbon Resources Conversion Vol. 2 ( 1 ) page： 13 - 22 2019.4

Language：Japanese Publishing type：Research paper (scientific journal) Publisher：Carbon Resources Conversion

Inherent metallic species retained by coal char or coke, such as Na and Ca, behave as catalysts in gasification. The char/coke normally contains inherent SiO2, which can react with the inherent catalysts to form silicates, resulting in catalyst deactivation over the range of pyrolysis, carbonization and gasification, and thereby reducing the char/coke reactivity. The present authors simulated the inherent catalyst deactivation experimentally by blending a Victorian lignite with SiO2, briquetting the SiO2/lignite blend, carbonizing the briquette, and then gasifying the coke with CO2. The kinetic analysis of the gasification employed a comprehensive model, which assumed progress in parallel of non-catalytic and catalytic gasification. The model quantitatively described the measured kinetics of the coke gasification with different SiO2 contents over a range of coke conversion up to 99.9%. The kinetic analysis revealed that the SiO2 deactivated substantial and entire portions of the most active catalyst and its precursor, respectively, before the gasification (i.e., during the carbonization). The catalyst deactivation also occurred during the gasification, but mainly following a self-deactivation mechanism that involved no silicates formation.

DOI： 10.1016/j.crcon.2018.09.002

An approach for quantifying transferable hydrogen in pyrolyzing coals Reviewed

Norinaga K., Fukuoka T., Machida H., Zhang W.

36th Annual International Pittsburgh Coal Conference: Clean Coal-Based Energy/Fuels and the Environment, PCC 2019 2019

Norinaga K., Nishio H., Khuyen T., Machida H.

36th Annual International Pittsburgh Coal Conference: Clean Coal-Based Energy/Fuels and the Environment, PCC 2019 2019

An approach for quantifying transferable hydrogen in pyrolyzing coals Reviewed

Norinaga K, Fukuoka T, Machida H, Zhang W

36th Annual International Pittsburgh Coal Conference: Clean Coal-Based Energy/Fuels and the Environment, PCC 2019 2019

Reducing energy required for CO<inf>2</inf> separation and recovery process by employing phase separation solvents Reviewed

Norinaga K, Nishio H, Khuyen T, Machida H

36th Annual International Pittsburgh Coal Conference: Clean Coal-Based Energy/Fuels and the Environment, PCC 2019 2019

No.2-19 Reducing energy required for CO2 separation/recovery process by employing amine/ether mixed absorbent Reviewed

MACHIDA Hiroshi, NISHIO Hitoshi, KHUYEN Tran, NORIANGA Koyo, ESAKI Takehiro

Proceedings of Conference on Coal Science Vol. 55 ( 0 ) page： 84 - 85 2018.10

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

It has been recognized that the CO2 separation and recovery process accounts around 60% of the total cost for operating CO2 capture and storage (CCS). The CO2 chemical absorption with a conventional amine solvent like monoethanol amine requires around 4 GJ/t-CO2 for CO2 recovery. Recently we developed phase separation solvent system which consists of not only amine but also hydrophobic solvent, ether. This system, before CO2 absorption, we have single phase, while after CO2 absorption, we have phase separation, one is CO2 rich phase and the other is CO2 lean phase. We can expect that the energy can significantly be reduced because it is not necessary to regenerate whole solvent but only the CO2 rich phase is to be regenerated. In this study, we examined the phase phenomena for 9 types of amine and a hydrophobic solvent mixture before and after CO2 absorption to find phase separation solvent system to minimize energy for CO2 recovery. Based on the observation, the mechanism for the phase separation and solvent regeneration is also discussed.

DOI： 10.20550/jiesekitanronbun.55.0_84

No.2-30 Chemical structure of coal and pyrolysis char and Quantitative evaluation of gas generation characteristics during pyrolysis Reviewed

FUKUOKA Tetsuya, MACHIDA Hiroshi, NORINAGA Koyo

Proceedings of Conference on Coal Science Vol. 55 ( 0 ) page： 110 - 111 2018.10

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

Changes in the chemical structure of coal during the dry distillation process and the composition and production characteristics of volatile components are important factors related to the mechanism of caking property development and the physical properties of coke masses and analyzed by various methods. However, up to now, analysis of volatile components and structural analysis of solid char are mostly performed individually, and it is difficult to combine both and to obtain quantitative knowledge on the thermal decomposition reaction mechanism. In this study, we tried to measure composition of dry distillation for caking coal and subbituminous coal using online gas analysis, and analyze changes of coal chemical structure using several spectroscopic methods (NMR, FT-IR, XPS etc.), integrated the obtained information to combine the former and the latter, and attempted to obtain new understanding of the coal dry distillation mechanism.

DOI： 10.20550/jiesekitanronbun.55.0_110

Computational Study on the Thermal Decomposition of Phenol-Type Monolignols Reviewed

Yuki Furutani, Yuki Dohara, Shinji Kudo, Jun-Ichiro Hayashi, Koyo Norinaga

International Journal of Chemical Kinetics Vol. 50 ( 4 ) page： 304 - 316 2018.4

Language：English Publishing type：Research paper (scientific journal) Publisher：John Wiley and Sons Inc.

A detailed chemical kinetic model has been developed to theoretically predict the pyrolysis behavior of phenol-type monolignol compounds (1-(4-hydroxyphenyl)prop-2-en-1-one, HPP
p-coumaryl alcohol, 3-hydroxy-1-(4-hydroxyphenyl)propan-1-one, HHPP
1-(4-hydroxyphenyl)propane-1,3-diol, HPPD) released from the primary heterogeneous pyrolysis of lignin. The possible thermal decomposition pathways involving unimolecular decomposition, H-addition, and H-abstraction by H and CH3 radicals were investigated by comparing the activation energies calculated at the M06–2X/6–311++G(d,p) level of theory. The results indicated that all phenol-type monolignol compounds convert to phenol by side-chain cleavage. p-Coumaryl alcohol decomposes into phenol via the formation of 4-vinylphenol, whereas HPP, HHPP, and HPPD decompose into phenol via the formation of 4-hydroxybenzaldehyde. The pyrolytic pathways focusing on the reactivity of the hydroxyl group in HPP and producing cyclopentadiene (cyc-C5H6) were also investigated. The transition state theory (TST) rate constants for all the proposed elementary reaction channels were calculated at the high-pressure limit in the temperature range of 300–1500 K. The kinetic analysis predicted the two favorable unimolecular decomposition pathways in HPP: the one is the dominant channel below 1000 K to produce cyc-C5H6, and the other is above 1000 K to yield phenol (C6H5OH).

DOI： 10.1002/kin.21164

Characteristic Properties of Lignite to Be Converted to High-Strength Coke by Hot Briquetting and Carbonization Reviewed

Shinji Kudo, Aska Mori, Gentaro Hayashi, Takuya Yoshida, Noriyuki Okuyama, Koyo Norinaga, Jun-Ichiro Hayashi

Energy and Fuels Vol. 32 ( 4 ) page： 4364 - 4371 2018.4

Language：English Publishing type：Research paper (scientific journal) Publisher：American Chemical Society

A sequence of hot briquetting and carbonization (HBC) is a promising technology for the production of coke with a high mechanical strength from lignite, but factors affecting the coke strength have not yet been fully understood. The HBC cokes prepared from 12 lignites in this study showed diverse tensile strength (e.g., from 0.2 to 31.2 MPa in the preparation at 200 °C and 112 MPa for hot briquetting and 1000 °C for carbonization), and the coke strengths could not be explained by differences in commonly used structural properties of the parent lignites, such as elemental composition and contents of volatile matter/fixed carbon and ash. In this study, two methods were proposed for correlating the coke strength with the lignite properties, which employed the chemical structure analyzed by solid-state 13C nuclear magnetic resonance or the volumetric shrinkage during carbonization. A stronger coke was obtained from lignite that contained more aliphatic carbons (less aromatic carbons) or shrank more considerably. These characteristics contributed to intensified compaction of lignite in the briquetting and suppression of the formation of large pores, which are a cause of coke fracture. Two empirical equations, predicting the coke strength from the parameters of lignite properties, were established to be criteria for selection of lignite as HBC coke feedstock, although further investigation with more experimental data would be necessary for the validation.

DOI： 10.1021/acs.energyfuels.7b03155

CO2 Gasification of Sugar Cane Bagasse: Quantitative Understanding of Kinetics and Catalytic Roles of Inherent Metallic Species Reviewed

Zayda Faizah Zahara, Shinji Kudo, Daniyanto, U. P.M. Ashik, Koyo Norinaga, Arief Budiman, Jun-Ichiro Hayashi

Energy and Fuels Vol. 32 ( 4 ) page： 4255 - 4268 2018.4

Language：English Publishing type：Research paper (scientific journal) Publisher：American Chemical Society

A total of 18 chars from the pyrolysis of six trios of sugar cane bagasses (SCBs
original, water-washed, and acid-washed) were gasified with CO2 at 900 °C, aiming at a quantitative description of the rate of gasification catalyzed by inherent metallic species and a correlation of the catalytic activity and its change during the gasification with the metallic species composition. The measured kinetics was described quantitatively over a range of char conversion, 0-0.999, by a model that assumed progress in parallel of the catalytic gasification and non-catalytic gasification, together with the presence of a catalytic precursor and three to four types of catalysts having different activities and deactivation characteristics. A series of regression analyses was scrutinized and reached expression of initial catalytic activity as a linear function of Na, K, Ca, Fe, and Si concentrations in the char with a correlation factor (r2) of &gt
0.98. The catalyst precursor contributed fully by water-soluble Na, K, and Ca. Si was responsible for the catalyst deactivation during the pyrolysis but not during the gasification. The chars produced from original SCBs followed a linear relationship between the initial catalytic deactivation rate and initial activity (r2 &gt
0.99), while such a linear relationship was not valid for those formed from the water-washed SCBs. This was explained mainly by more rapid deactivation of the Fe catalyst in the chars from water-washed SCBs than that in the chars formed from the original SCBs. Na and K in char from the original SCBs, originating from the water-soluble SCBs, chemically interacted with the Fe catalyst, slowing its deactivation.

DOI： 10.1021/acs.energyfuels.7b03147

Energy-saving CO<inf>2</inf> Capture Process Using Phase Separation Type Solvent by Aqueous (amine + ether) Solution Reviewed

Machida H., Takehiro E., Yamaguchi T., Norinaga K., Kishimoto A., Akiyama K., Nishimura M.

GHGT 2018 - 14th International Conference on Greenhouse Gas Control Technologies 2018

Language：English Publishing type：Research paper (scientific journal) Publisher：GHGT 2018 - 14th International Conference on Greenhouse Gas Control Technologies

We have developed the phase separation solvent for CO2 capture. Our developed solvent consists amine, organic solvent and water and shows single liquid phase before CO2 absorption though it shows two liquid phases after CO2 absorption. Feature of phase separation solvent is reducing temperature difference between absorber and stripper. We apply the heat pump system for CO2 separation and evaluate the energy consumption. Low temperature swing process saves energy requirement for CO2 capture process with highly-effective reaction-heat recovering. To evaluate the CO2 capture system with our solvent, screening test for amine and organic solvent combination and CO2 solubility measurement were examined. In the phase separation test, three types of solvents were obtained by combining amine and ether, that is, no phase separation with CO2 scrubbing, phase separation with CO2 scrubbing, and thoroughly immiscible. The phase behaviour depends on the hydrophobicity of amines or organic solvents, and the types of solvents were classified using the hydrophobic parameter.

Current situation and future scope of biomass gasification in Japan Open Access

Furutani, Y, Norinaga, K, Kudo, S, Hayashi, J.-I, Watanabe, T

Evergreen Vol. 4 ( 4 ) page： 24 - 29 2017.12

Language：Japanese Publishing type：Research paper (scientific journal) Publisher：Transdisciplinary Research and Education Center for Green Technologies, Kyushu University

In this study, we investigated current situation of biomass gasification plants in 5 cities (c.a. Murayama City, Chichibu City, Ueno Village, Oshu City and Yamaguchi City) in Japan, and make R&D policy proposals to expand the biomass gasification plants. Four cities have commonly promoted the efficient heat utilization such as snow melting, drying the wood and supplying hot water into mushroom bed and hot spring. However, heat utilization is limited in a small area because heat loss is generated during the long-distance transportation. In order to obtain energy forms suitable for the long-distance transportation, such as hydrogen gas and electricity, the R&D of biomass gasification with hydrogen production or combined with Solid Oxide Fuel Cell (SOFC) should be promoted in the future.

DOI： 10.5109/1929681

7-2-4 Development of energy-saving CO2 capture process using phase separation absorbent Reviewed

MACHIDA Hiroshi, ESAKI Takehiro, YAMAGUCHI Tsuyoshi, HORIZOE Hirotoshi, NORINAGA Koyo, KISHIMOTO Akira, MATSUOKA Akira, AKIYAMA Katsuya, NISHIMURA Makoto

Proceedings of the Annual Conference of The Japan Institute of Energy Vol. 26 ( 0 ) page： 228 - 229 2017

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

Phase separation type CO2 capture solvent was developed which transforms into two liquid phases after CO2 absorption. At first, we checked the phase phenomena of 9 types of amine and 3 types of polyether combinations. There shows three types; keeping one liquid phase before and after CO2 absorption, transforming into two liquid phase after CO2 absorption, forming initially two liquid phases. CO2 solubility of the developed phase separation solvent was measured. The results show that the phase separation solvent can reduce the temperature difference between absorber and desorber than that of conventional amine solvent. Required energy for CO2 capture using phase separation solvent was estimated under 2.0 GJ/ton-CO2.

DOI： 10.20550/jietaikaiyoushi.26.0_228

P-3-3 Detailed Chemical Kinetic Modeling of Primary and Secondary Pyrolysis of Lignin Reviewed

FURUTANI Yuki, DOHARA Yuki, KUDO Shinji, HAYASHI Jun-ichiro, NORINAGA Koyo

Proceedings of the Annual Conference of The Japan Institute of Energy Vol. 26 ( 0 ) page： 268 - 269 2017

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

A set of lignin pyrolysis processes involving primary pyrolysis and secondary vapor-phase reactions were described with a detailed chemical kinetic model (DCKM). The DCKM of primary pyrolysis, which characterizes lignin structures as three model compounds, predicted the yields of volatiles (c.a. 22 gas species and 10 monolignols) derived from primary pyrolysis. The original DCKM of secondary vapor-phase reactions did not involve the kinetic database on vapor-phase reaction of monolignols. Thus, the pyrolytic pathways of 1-(4-hydroxy-3,5-dimethoxyphenyl)prop-2-en-1-one (HDPP) accounted for 60 - 80 wt% of total monolignol species were proposed, and total 230 elementary reaction rate constants obtained by ab initio theory were added into the original kinetic database. The simulation of secondary vapor-phase reaction was performed using the volatile composition predicted by the DCKM of primary pyrolysis as a boundary condition. The established kinetic models successfully reproduced the yields of H2O and char, but at high temperature overestimated tar yield and underestimated CO yield. This is probably due to the insufficient kinetic model of the secondary vapor phase reaction, which did not include the decomposition pathways of the monolignols except for HDPP.

DOI： 10.20550/jietaikaiyoushi.26.0_268

A Supported Ni Catalyst Produced from Ni-Al Hydrotalcite-Like Precursor for Reduction of Furfuryl Alcohol to Tetrahydrofurfuryl Alcohol by NaBH4 in Water Reviewed

Ren, DZ; Wang, JY; Jiang, XL; Song, ZY; Norinaga, K; Huo, ZB

CHEMISTRYSELECT Vol. 6 ( 4 ) page： 551 - 556 2021.1

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

Tetrahydrofurfuryl alcohol (THFA) is a kind of high value-added compound in industry, which can be obtained from biomass chemical engineering. However, Synthesis of THFA under mild condition with green hydrogen donors remains a big challenge. In this article, a supported Ni catalyst derived from Ni−Al hydrotalcite-like compounds (HTs) as precursors for the reduction of furfuryl alcohol (FA) into THFA with NaBH4 as reducing agent in water was first reported. As a result, Ni/Al2O3−HT exhibited high catalytic activity for the transformation, and THFA was achieved in 100 % yield at 60 °C for 60 min. Moreover, Ni/Al2O3−HT could be recycled at least seven times without the loss of its activity. Under optimized conditions, the reduction reaction of several furan and ketone compounds was investigated. A possible mechanism for the reduction of FA to afford THFA was also proposed.

DOI： 10.1002/slct.202003543

Lattice Boltzmann simulation of multicomponent reaction-diffusion and coke formation in a catalyst with hierarchical pore structure for dry reforming of methane Reviewed Open Access

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

CHEMICAL ENGINEERING SCIENCE Vol. 229 2021.1

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

In order to further enhance catalytic activity and inhibit carbon formation, the hierarchical structure-performance relationship has been investigated in dry reforming of methane (DRM). A modified random generation of macro-mesopores (RGMMP) algorithm was adopted to model the structure of the catalyst with macropore and mesopore. Based on multi-component non-continuum reaction-diffusion lattice Boltzmann model, the effects of three hierarchical pore geometrical parameters, namely the catalyst porosity, the ratio of mesopore volume to macropore volume and the ratio of average macropore diameter to average mesopore diameter, on coke formation and catalytic performance were investigated to elucidate the deactivation and reaction-diffusion mechanism of the catalyst in DRM. Based on the competitive relationship between heterogeneous reaction and intraparticle diffusion, the optimal values to define hierarchical pore structure have been identified, which provides maximum catalytic performance and coking resistance for a reaction condition.

DOI： 10.1016/j.ces.2020.116105

Prediction of Phase Behavior of CO2 Absorbents Using Conductor-like Screening Model for Real Solvents (COSMO-RS): An Approach to Identify Phase Separation Solvents of Amine/Ether/Water Systems upon CO2 Absorption Reviewed

Nakaoka, M; Tran, KVB; Yanase, K; Machida, H; Norinaga, K

INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH Vol. 59 ( 42 ) page： 19020 - 19029 2020.10

Language：Japanese Publishing type：Research paper (scientific journal) Publisher：Industrial and Engineering Chemistry Research

Developing energy-saving absorbents for carbon dioxide (CO2) is essential for improving carbon capture and storage (CCS) technologies. Recently, we have designed phase separation solvents, which can significantly reduce the regeneration energy for CO2 capture and separation down to 1.6 GJ/ton-CO2 [ Machida, H.; et al. Int. J. Greenhouse Gas Control2018, 75, 1-7 ]. For further developing better solvents, this paper studied a theoretical approach with conductor-like screening model for real solvents (COSMO-RS) to screen the amine/ether/water systems to identify phase separation solvents upon CO2 absorption. In this work, liquid-liquid equilibria of 21 amine/ether/water systems were determined both before and after CO2 absorption. Experimentally, it has already been demonstrated that the phase behavior of these systems is classified into three categories: phase separation type, miscible type, and immiscible type. This study demonstrates that the octanol/water partition coefficient is empirically able to search for a combination of amine and ether compounds, in which the system exhibits the phase separation behavior by absorbing CO2. The COSMO-RS calculations successfully reproduced experimental phase behavior with a rate of agreement of more than 80% by accounting the following two factors: (i) ion pairing for the description of the association/dissociation state for ionic species and (ii) relevant low-lying conformations of ether and amine, which are rationalized by experiments such as conductivity and excess enthalpy measurements. Moreover, we also validated the ability of the COSMO-RS calculation to qualitatively describe the compositions of 2-(ethylamino)ethanol, diethylene glycol diethyl ether, and water in CO2-rich and CO2-lean phases at varying CO2 loading conditions.

DOI： 10.1021/acs.iecr.0c03233