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Binary catalyst composed of alkali metal and alkaline earth metal was widely used to overcome the shortcoming of single-metal catalyst. However, the synergistic mechanism between components remains unclear. In present work, sodium and calcium were loaded into the coal char individually or together. TGA gasification was used to investigate catalytic effect. In order to evaluate catalytic mechanism, Raman spectra of gasification residue, Raman spectra of quenched slag and phase composition at thermodynamic equilibrium were obtained. Loading of sodium or calcium significantly increased gasification rate of coal char and catalytic effect of sodium was better than calcium. Above 900 °C, catalytic effect of sodium-calcium binary catalyst was better than that of single catalyst, and gasification residue of binary catalyst loaded char had more calcium silicate and less sodium silicate than gasification residue of single-metal catalyst loaded char. It was speculated that calcium reacted first with silica in coal to inhibit sodium inactivation. Raman spectra of quenched slag and theoretical calculation showed that silica preferentially reacted with calcium oxide to form calcium silicate in calcium oxide-sodium carbonate-silica system, which proved above speculation. Furthermore, the significant catalytic activity of binary catalysts inhibited the graphitization evolution of carbon structure during char gasification, which is conducive to the improvement of gasification rate. [ABSTRACT FROM AUTHOR]

• Effects of pyrolysis temperature, residence time and atmosphere were investigated. • Release of AAEMs was associated with char structure evolution in rapid pyrolysis. • CO 2 promoted Na release in early stage and Ca and Mg release in late stage. The release law of alkali and alkaline earth metals (AAEMs) during coal pyrolysis is crucial for controlling scaling, corrosion and slagging in the utilization of high AAEMs coal. To approximate entrained-flow bed gasification process, a free-falling reactor was used for coal pyrolysis to study the release characteristics of AAEMs in nascent char. Effects of pyrolysis temperature, residence time and atmosphere were investigated. The cumulative release of Na, Ca and Mg at 1100 °C was 68.0%, 47.5% and 69.8%, respectively. As pyrolysis temperature increased from 900 °C to 1100 °C, the release of Na, Ca and Mg increased by 7.0 %, 3.5% and 5.3%, respectively. The cumulative release of AAEMs increased with the pyrolysis residence time, but the release rate decreased significantly in middle and late stages. The promoted thermal decomposition of functional groups by CO 2 resulted in a lower char yield. CO 2 promoted Na release in early stage and Ca and Mg release in late stage. Furthermore, release of AAEMs was associated with char structure evolution in rapid pyrolysis. The presence of CO 2 , high temperature and prolonged residence time led to enhanced particle fragmentation, increased surface cracks, and intensified thermal decomposition of functional groups, resulting in the migration of AAEMs in carbon matrix to char surface and the release of AAEMs organically bound to carbon matrix. [ABSTRACT FROM AUTHOR]

• In-situ Raman spectroscopy was innovatively used to characterize carbon structure. • AAEM promoted continuous breaking/reforming of bonds in polycondensation. • Inherent AAEM promoted the miniaturization of carbon crystal structure. Inherent minerals, especially alkali and alkaline earth metals (AAEM), are reactive constituents that interact with organic matter during pyrolysis and have significant effects on thermal characteristics and carbon structure evolution of char. The pyrolysis of raw and leached coal samples was conducted by using thermogravimetric analyzer and in-situ Raman system to explore the effects of content and chemical form of AAEM on pyrolysis characteristics and carbon structure evolution of single char particle. The water-soluble and ion-exchangeable AAEM promoted continuous breaking/reforming of bonds between alkyl substitutional groups and aromatic ring systems, resulting in the delay of volatiles release and orderly evolution of carbon structure during pyrolysis. The effects of water-soluble AAEM was more severe, because the divalent alkaline earth metal bonds to carbon was much more stable than the monovalent alkali metal for the inherent AAEM participated in the polycondensation reaction. Besides, the ion-exchangeable AAEM inhibited the generation of cross-linked structures more effectively than water-soluble AAEM, because ion-exchangeable AAEM existed in the form of AAEM-carboxylates and delayed the thermal decomposition. Moreover, the inherent AAEM promoted the miniaturization of carbon crystal structure in the carbon matrix, forming char with disordered carbon structure. [ABSTRACT FROM AUTHOR]

• 300 °C torrefaction reduced gasification reactivity mainly in midterm and late stage. • Low-temperature torrefaction had slight effect on char gasification reactivity. • Gasification kinetics were analyzed based on the gas-solid reaction methods. • Pathways of char structure evolution changed after 800 °C pyrolysis. • Gasification reactivity decreased significantly for chars pyrolyzed after 800 °C. In this study, the effect of torrefaction on the gasification reactivity of chars from raw and torrefied biomass was investigated. Three torrefaction temperatures and four pyrolysis temperatures were taken into consideration. It was found that the severe torrefaction (300 °C) would reduce the char gasification reactivity by at least 19% according to the normalized gasification rate. Moreover, the reduction of gasification reactivity appeared after the midterm stage. The gasification reaction were further analyzed by nucleation/growth model and model-free method. The activation energy increased by ~80 kJ/mol with conversion, indicating an enhancement of the reaction resistance. Furthermore, 800 °C pyrolysis was found to be a turning point, beyond which the gasification reactivity reduced significantly. These reactivity changes were implied by the bio-char structure evolution and active alkali and alkaline earth metals (AAEMs) contents variations. The research results provide insights into the effect of torrefaction on biomass gasification. [ABSTRACT FROM AUTHOR]

[Display omitted] • An integration of pilot-scale HTC, gasification, and anaerobic digestion for EFB conversion was investigated. • Inherent AAEMs have significant effects on gasification products. • CO and H 2 were enhanced under CO 2 /O 2 gasification. • Liquid products from HTC can be utilized for methane production via anaerobic digestion. • The mass and energy balance revealed that the whole process could be feasible. In the context of evolving a circular economy for the palm-oil industry, this article presents a study of oil-palm empty fruit bunch (EFB) conversion and utilization within a palm-oil mill. Pilot-scale hydrothermal carbonization (HTC), washing and gasification processes, as well as anaerobic digestion of the HTC liquid product were investigated. Results showed that the fuel properties of hydrochars had improved. In terms of air gasification, char and tar products accounted for 22.7–33.8 % and 17.3–28.8 %, respectively while CO 2 /O 2 gasification resulted in 31.3–36.6 % for char and 8.5–30.8 % for tar. In general, hydrochar (HT-EFB) gave the lower tar content compared to washed hydrochar (HTW-EFB) due to the catalytic effects of alkali and alkaline earth metals. Major tar components from HT-EFB and HTW-EFB were aliphatic and monoaromatic hydrocarbons, respectively. Syngas products from air gasification of hydrochars were 39.9–56.5 %, 11.4–21.4 %, and 9.0–14.4 % for CO, H 2 and CH 4 , respectively while CO 2 /O 2 gasification products yielded 45.1–56.6 %, 11.6–24.3 %, and 9.4–14.0 % for CO, H 2 and CH 4 , respectively. The lower heating value of syngas was in the range of 4.7–6.6 MJ/Nm3 and cold gas efficiency was approximately 39.1–55.1 %. The cumulative methane from the liquid products amounted to 213.8 and 154.5 L/kg COD for food/microorganism ratios of 1:2 and 1:3, respectively. The mass and energy balance showed that the whole process is promising for future commercialization. [ABSTRACT FROM AUTHOR]

Hydrothermal carbonization (HTC) can improve biomass quality in both physical and chemical aspects for energy application. This study aims to investigate the characteristics and reactivities of rape straw (RS) hydrochars. Hydrochars were prepared at 160–240 °C with residence time of 15–120 min. Mass yield, energy yield, microstructure, functional group and migration of alkali and alkaline earth metals (AAEMs) were studied to evaluate the influence of different conditions on properties of hydrochar. The results showed that O/C and H/C ratio decreased, while the higher heating value (HHV) increased with increasing temperature and residence time. The effect of increasing temperature on hydrochar properties was more significant than residence time. The structure was changed, and hydrochar possessed a more stable form after the aromatization reaction. For the gasification reactivity of hydrochar, decomposition rate curves showed that the peak of pyrolysis and gasification moved to a higher temperature region with the increasing of HTC temperature because of the developed aromatic structures in hydrochar. The pyrolysis activation energy decreased from raw RS 71.68 to 41.03 kJ/mol in 240 °C, while gasification activation energy increased from 80.42 to 251.30 kJ/mol. Moreover, it was found that HTC can reduce the content of AAEMs efficiently and the best removal condition is 200 °C. Ca content dropped to a minimum value at 200 °C and then increased at higher temperature which may be caused by well-developed pore structure in hydrochars. This study provides basic data for comprehensive utilization of rape straw and migration mechanism of AAEMs in HTC process. [Display omitted] • The effects of HTC on RS structure and reactivity were quantitatively studied. • Temperature effect was more obvious than residence time during HTC. • Effects of HTC on kinetics of pyrolysis and gasification were studied separately. • Energy yield reached max at 180 °C, while AAEMs reached minimum at 200 °C. • The migration behavior of total and active AAEMs is studied. [ABSTRACT FROM AUTHOR]

Despite a small proportion of mineral in coal, inherent alkali and alkaline earth metals (AAEM) catalytically affected thermal conversion of coal. The gasification of raw and leached coal char was investigated by using an operando microscopic Raman spectroscopy to explore the effect of content and chemical form of the inherent AAEM on morphology and carbon structure evolution of a single particle during in-situ char gasification. The removal of water-soluble and ion-exchangeable AAEM reduced the R 0.5 of SF, NM and YN char by 53.31%, 49.09% and 35.02%, respectively. As a result, the shrinkage of leached coal char progressed slower than that of the raw coal char. Besides, both water-soluble and ion-exchangeable AAEM accelerated char gasification because of an inhibition of the orderly evolution of carbon structure. Higher gasification temperature weakened the catalytic performance of ion-exchangeable AAEM. With the consumption of carbon, carbon microcrystalline structure of the residual char tended to be ordered, which led to a decrease in active free carbon sites for gasification reaction. Kinetic analysis indicated both water-soluble and ion-exchangeable AAEM reduced the activation energy of SF, NM and YN char by 20.97, 20.82 and 9.38 kJ∙mol−1, respectively, and the effect of ion-exchangeable AAEM was more significant. • Coupling in-situ analysis of particle shrinkage and carbon structure was conduct. • Water-soluble AAEM had more significant effects on carbon structure evolution. • Catalytic performance of ion-exchangeable AAEM was better. • Evolution of carbon structure affected catalytic mechanism of AAEM. [ABSTRACT FROM AUTHOR]

The effects of alkali and alkaline earth metals (AAEM) on the component and distribution of products, gasification reactivity, catalytic mechanism and char-ash/slag transition during biomass gasification were reviewed. Biomass is mainly composed of cellulose, hemicellulose and lignin, and has a much higher AAEM species content than coal. The influence of inherent AAEM on biomass gasification is closely related to the gasification agent and operating conditions. To remove tar and reduce soot, interest has grown on the subject of AAEM catalysis for biomass gasification. Therefore, component and distribution of products and gasification reactivity in inherent and loaded AAEM catalytic biomass gasification were reviewed. Furthermore, the effects of AAEM on biomass conversion can be divided into homogeneous and heterogeneous catalytic effects based on the phase states involved in chemical reactions. Three main mechanisms including oxygen transfer mechanism, active site mechanism and catalytic desorption mechanism are summarized to understand the heterogeneous catalytic process. The attribution to the promotion of the homogeneous reaction is concluded as the volatile gaseous AAEM catalyzed the water-gas shift reaction and the hydrocarbon reforming reaction. In addition, the effects of AAEM content on char-ash/slag transition in biomass gasification were also reviewed. • Biomass component gasification characteristics are summarized and compared. • Product distribution and reactivity of biomass gasification are reviewed. • Three main AAEM catalytic biomass gasification mechanisms are summarized. • Effect of AAEM on char-ash/slag transition during gasification is discussed. [ABSTRACT FROM AUTHOR]