研究者詳細 - 則永　行庸

Quantitative Description of Catalysis of Inherent Metallic Species in Lignite Char during CO2 Gasification 査読有り

Modelling of CO<inf>2</inf> solubility in phase separation solvent composed of amine/ether/water system for CO<inf>2</inf> capture 査読有り Open Access

Machida, H., Ando, R., Esaki, T., Yamaguchi, T., Norinaga, K.

Journal of Molecular Liquids 292 巻 2019年10月

Halim, N; Ashik, UPM; Gao, XP; Kudo, S; Sanwani, E; Norinaga, K; Hayashi, J

ENERGY & FUELS 33 巻 ( 7 ) 頁： 5996 - 6007 2019年7月

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：Energy and Fuels

Chars from 20 lignite samples were prepared from two types of original lignites by multistage removal of inherent metallic species and subsequent pyrolysis and then were gasified with CO<inf>2</inf>. A kinetic model, which assumed the progress of noncatalytic and catalytic gasification in parallel, quantitatively described the time-dependent changes in char conversion up to 0.999 for all the chars by employing multicatalytic species having different initial activities and deactivation kinetics. A single piecewise linear function, which followed a nucleation-growth mechanism of the catalysts, showed the relationship between the total concentration of Na, K, Ca, and Fe and the initial total catalytic activity (ICA-2) for the chars. The overall rate of catalyst deactivation (ICD-2) was given by a single linear function of ICA-2 and a factor for the composition of metallic species. This function was also applicable to previously reported ICA-2/ICD-2 relationships for chars from lignite and biomass, showing fast deactivation of Fe catalyst and an important role of Mg in the promotion of catalyst deactivation.

DOI： 10.1021/acs.energyfuels.9b00465

Production of High-strength Cokes from Non-/Slightly Caking Coals. Part I: Effects of Coal Pretreatment and Variables for Briquetting and Carbonization on Coke Properties 査読有り Open Access

Matoba, M; Kudo, S; Mori, A; Norinaga, K; Uchida, K; Dohi, Y; Uebo, K; Hayashi, J

ISIJ INTERNATIONAL 59 巻 ( 8 ) 頁： 1440 - 1448 2019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：ISIJ International

In continuation of the present authors' studies on production of high strength coke from lignite by sequential binderless hot briquetting and carbonization, this study has been carried out aiming at proposing methods to produce high strength coke from non-/slightly caking coals of subbituminous to bituminous rank. This paper firstly demonstrates preparation of cokes with cold tensile strengths above 10 MPa from two single non-caking coals (particle size; < 106 μm) by applying briquetting at temperature and mechanical pressure of over 200°C and 100 MPa, respectively. Such strength of coke is obtained over a wide range of heating rate, 3-30°C/min, during carbonization with final temperature of 1 000°C. Then, a simple pretreatment, fine pulverization of coal to particle sizes smaller than 10 or 5 μm, is examined. This pretreatment enables to prepare coke with tensile strength even over 25 MPa, by decreasing porosity of resulting coke and more extensively the size of macropores simultaneously. The coke strength changes with carbonization temperature having a particular feature; significant development of strength at 600-1 000°C, i.e., after completion of tar evolution, in which macropores and non-porous (dense) part of coke shrink in volume, inducing bonding and coalescence of particles and thereby arising the strength.

DOI： 10.2355/isijinternational.ISIJINT-2018-819

Quantitative Analyses of Chemical Structural Change and Gas Generation Profile of Coal upon Heating toward Gaining New Insights for Coal Pyrolysis Chemistry 査読有り Open Access

Fukuoka, T; Takeda, N; Zhang, L; Machida, H; Zhang, W; Watanabe, M; Nishibata, Y; Hayashi, J; Norinaga, K

ISIJ INTERNATIONAL 59 巻 ( 8 ) 頁： 1376 - 1381 2019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：ISIJ International

Chemical structure of coal is evolutionary changed during pyrolysis that accompanies gas release. The chemical structural change and gas formation profiles play important roles in determining caking property and physical properties such as strength and size of the resultant coke. However, analyses of volatile components and structural analysis of solid char have been mostly performed individually, and it is difficult to combine both and to obtain quantitative understanding on the thermal decomposition of coal at mechanistic level. In this study, simultaneous analyses of solid chemical structures of the heat treated coals and gas formation profiles were conducted for two kinds of coals that were pyrolyzed at an identical condition. On-line gas analysis with a quadrupole mass spectrometer and spectroscopic methods (NMR and FT-IR) were employed for quantitative evaluation of gas formation characteristics and solid chemical structure, respectively. The information obtained were then integrated to acquire new insight for coal pyrolysis mechanism. Here an approach to quantify the transferable hydrogen that contributes to stabilize radicals formed in pyrolyzing coal was proposed. It includes the quantitative assessment of aromatic cluster growth, decomposition of hydroxyls, and releases of hydrogen and pyrolytic water into gas phase. The proposed approach suggested that a bituminous coal that exhibits plasticity during pyrolysis had 3.5 mol/kg-coal transferable hydrogen, whereas the amount of transferable hydrogen of the sub-bituminous coal, a non-caking coal, was 1.3 mol/kg-coal, during pyrolysis up to 500°C.

DOI： 10.2355/isijinternational.ISIJINT-2018-816

Production of High-strength Cokes from Non-and Slightly Caking Coals. Part II: Application of Sequence of Fine Pulverization of Coal, Briquetting and Carbonization to Single Coals and Binary Blends 査読有り Open Access

Uchida, K; Kudo, S; Mori, A; Ashik, UPM; Norinaga, K; Dohi, Y; Uebo, K; Hayashi, J

ISIJ INTERNATIONAL 59 巻 ( 8 ) 頁： 1449 - 1456 2019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：ISIJ International

Sequential coal briquetting and carbonization was applied to preparation of cokes from 9 non- or slightly caking coals with carbon contents (f<inf>C</inf>) of 67-85 wt%-daf. Coal pulverization to sizes of <106 μm and briquetting at 40°C enabled to prepare cokes with tensile strength (σ) over 10 MPa from 4 coals with f<inf>C</inf> of 82-85 or 67 wt%-daf. Then, by introducing fine pulverization to sizes of < 10 μm before the briquetting, 7 coals were converted successfully into cokes with σ = 11-25 MPa. Increasing the briquetting temperature to 240°C further increased σ to 19-35 MPa for all the 9 coals. It was thus demonstrated that the hot briquetting of finely pulverized coal was a method to prepare high strength coke regardless of the rank of parent coal. Cokes were also prepared from 14 binary coal blends. All the cokes prepared by applying the fine pulverization and hot briquetting had σ of 20-35 MPa, which agreed well with that calculated by weighted average of those from the component coals. On the other hand, positive and also negative synergistic effects of blending occurred when blends were briquetted at 40°C. Characteristics of bonding/ coalescence among particles of different types of coals were responsible for such synergies.

DOI： 10.2355/isijinternational.ISIJINT-2018-847

An approach for quantifying transferable hydrogen in pyrolyzing coals 査読有り

Norinaga K

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

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

Norinaga K

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

An approach for quantifying transferable hydrogen in pyrolyzing coals 査読有り

Norinaga K

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

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

Norinaga K

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

Characteristics of gas evolution profiles during coal pyrolysis and its relation with the variation of functional groups 査読有り Open Access

Zhang L., Qi S., Takeda N., Kudo S., Hayashi J., Norinaga K.

International Journal of Coal Science and Technology 5 巻 ( 4 ) 頁： 452 - 463 2018年12月

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：International Journal of Coal Science and Technology

Strict relation between the substituents or functional groups attached to the coal macromolecules and the generation of the volatile products, e.g., CH<inf>4</inf>, H<inf>2</inf>O, CO, CO<inf>2</inf>, etc., during the coal pyrolysis is an important but confusing subject. In this paper, quadrupole mass spectrometry, gas chromatography, and 13C nuclear magnetic resonance are applied to real-time monitoring the formations of volatile products, off-line quantitative determination of the total products from the pyrolysis of a sub-bituminous coal (SC), and the changes of diverse substitents in the SC along with coke foamation, respectively. These measurements are also performed for the pyrolysis of a caking coal to contrast SC. The qualitative and quantitative data reveal that, during coal pyrolysis, the functional groups related with the formation of CO, i.e., ether, carbonyl, and anhydride, can directly generate CO via bond breaking, or take a detour of the formation of other intermediates via condensation and recombination firstly. Moreover, the formations of CO<inf>2</inf> and CH<inf>4</inf> are related to the direct removal of -COO- and -CH<inf>3</inf>, respectively.

DOI： 10.1007/s40789-017-0175-0

Open Access

Effects of HZSM-5 on volatile products obtained from the fast pyrolysis of lignin and model compounds 査読有り

Yang, HM; Norinaga, K; Li, J; Zhu, WY; Wang, HJ

FUEL PROCESSING TECHNOLOGY 181 巻頁： 207 - 214 2018年12月

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：Fuel Processing Technology

This study aimed to experimentally investigate the effect of HZSM-5 on the distribution of volatile products, especially carbon monoxide (CO), C<inf>1</inf>–C<inf>5</inf> hydrocarbons and aromatic hydrocarbons (AHs) during catalytic pyrolysis of lignin and lignin model compounds. Catechol was pyrolyzed using a two-stage tubular reactor (TS-TR) connected to a gas chromatography system over HZSM-5 at 550–950 °C. Forty-three products, including four inorganic gases, twenty C<inf>1</inf>–C<inf>5</inf> hydrocarbons, and nine AHs were quantified using three GC-columns. Results indicated that HZSM-5 accelerated the catechol conversion with a large amount of CO and AHs produced. C<inf>1</inf>–C<inf>5</inf> hydrocarbons were formed during non-catalytic pyrolysis of model compounds, and consumed quickly during HZSM-5 catalytic pyrolysis of catechol. Catalytic pyrolysis of phenol, guaiacol and syringol was carried out at 650 °C in the TS-TR over HZSM-5. HZSM-5 obviously promoted the conversion of lignin model compounds, and largely increased the yield of volatile products especially CO and AHs. Three lignin samples were also catalytically pyrolyzed over HZSM-5 in the TS-TR at 650 °C. HZSM-5 increased the yield of C<inf>2</inf>-C<inf>3</inf> hydrocarbons and AHs, and reduced the yield of oxygenated compounds. HZSM-5 could promote the formation of AHs (lower than 10 wt%) during lignin pyrolysis, but not as obviously as during model compounds pyrolysis (higher than 19 wt%). High yields of char and tar would account for the low catalytic efficiency of HZSM-5 during lignin pyrolysis.

DOI： 10.1016/j.fuproc.2018.09.022

Prediction of hot coke oven gas reforming by LES coupled with the extended flamelet/progress variable approach 査読有り

Yu, PL; Norinaga, K; Watanabe, H; Kitagawa, T

FUEL 231 巻頁： 234 - 243 2018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：Fuel

Large-eddy simulation (LES) coupled with the extended flamelet/progress variable approach (EFPV) has been performed to predict characteristics of reacting flows in a bench-scale hot coke oven gas (HCOG) reformer. In order to investigate the capability of capturing effects of operating conditions, simulations were carried out in two different cases in which the coke oven gas temperature and oxygen ratio were altered. Results showed that the LES coupled with the EFPV performed very well in terms of predicting temperature distribution as well as the temperature variation trend between the two cases. In addition, major species such as H<inf>2</inf>, CO, CO<inf>2</inf>, H<inf>2</inf>O and CH<inf>4</inf>, as well as minor species like benzene and some typical polycyclic aromatic hydrocarbons (PAH) were analyzed to illustrate their activities and dominant chemical events. With regards to the composition of the dry reformed gas, comparisons were made between the experimental data and the numerical simulation results, and reasonable results have been obtained. It has been confirmed that the general feature of the reacting flows in the HCOG reformer can be precisely captured by the present LES.

DOI： 10.1016/j.fuel.2018.05.104

Characteristic Properties of Lignite To Be Converted to High-Strength Coke by Hot Briquetting and Carbonization 査読有り

Kudo, S; Mori, A; Hayashi, G; Yoshida, T; Okuyama, N; Norinaga, K; Hayashi, J

ENERGY & FUELS 32 巻 ( 4 ) 頁： 4364 - 4371 2018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

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

Computational Study on the Thermal Decomposition of Phenol-Type Monolignols 査読有り

Furutani, Y; Dohara, Y; Kudo, S; Hayashi, JI; Norinaga, K

INTERNATIONAL JOURNAL OF CHEMICAL KINETICS 50 巻 ( 4 ) 頁： 304 - 316 2018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：International Journal of Chemical Kinetics

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 CH<inf>3</inf> 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-C<inf>5</inf>H<inf>6</inf>) 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-C<inf>5</inf>H<inf>6</inf>, and the other is above 1000 K to yield phenol (C<inf>6</inf>H<inf>5</inf>OH).

DOI： 10.1002/kin.21164