Raw Char Research Articles

In situ self-activation strategy for the synthesis of double-layered S/Cl co-doped sorbents for elemental mercury removal from oxy-fuel combustion flue gas

Mercury capture from oxy-fuel combustion flue gas remains an enormous challenge for carbon capture and storage because of the lack of cost-effective, sulfur-resistant and water-resistant sorbent. In this work, double-layered S/Cl co-doped sorbents (CDSs) were synthesized through an in situ self-activation method i.e. co-pyrolysis of waste tire and PVC plastic, which were adopted for elemental mercury (Hg0) immobilization from oxy-fuel combustion flue gas. A synergistic effect between waste tire and PVC plastic was observed during co-pyrolysis. For this reason, chlorine was successfully doped into the CDSs in the form of covalent chlorine and ionic chlorine. The CDSs showed high Hg0 removal efficiency (>80 %) over a wide temperature range (20–140 °C) and excellent sulfur and water resistance. Both the initial Hg0 adsorption rate and adsorption capacity of CDSs were far higher compared with raw tire char. The Hg0 removal mechanisms were further proposed, where Hg0 preferentially reacted with covalent chlorine instead of active sulfur species. Density functional theory calculations revealed that the Hg0 adsorption over CDSs was chemisorption with an adsorption energy of −249.85 kJ/mol. The synergistic effect between sulfur and chlorine was beneficial for the formation of HgCl2 whereas it had negligible effect on the formation of HgCl.

Catalytic influence of iron oxide (Fe2O3) on coal pyrolysis and char combustion at various temperatures

The conversion of coal into cleaner energy forms is essential for achieving sustainable development. This study investigates the role of Fe2O3 as a catalyst in enhancing the efficiency of coal pyrolysis and char combustion. A fixed-bed tube furnace (TF) was selected for pyrolysis, and a Thermogravimetric Analyzer coupled with Fourier Transform Infrared Spectroscopy (TG-FTIR) was used for combustion analysis. The produced syngas and tar were characterized using Gas Chromatography (GC) and Gas Chromatography-Mass Spectrometry (GC/MS). Our results show higher volatile release volume (VRV) from coal with catalyst compared with without catalyst and the rise with temperature within the 600–1000 ℃ range. Although hydrogen production decreased with the addition of the catalyst, at 1000 ℃, the catalyst's impact was negligible. The catalyst notably facilitated the breakdown of heavy aromatic rings in tar, eliminating triple-bond aromatic structures. In contrast, tar from raw coal exhibited a 20% yield of such structures. Scanning Electron Microscopy (SEM) revealed a cubic structure of Fe2O3 in char, with an increased surface area compared to raw coal char (338.75 m2/g vs. 313.51 m2/g). TG-FTIR analysis indicated a lower activation energy for catalysts with char combustion. Overall, Fe2O3 improves tar structure, increases char surface area, and lowers activation energy.

Enhancing Fuel Properties of Napier Grass via Carbonization: A Comparison of Vapothermal and Hydrothermal Carbonization Treatments

Napier grass is a herbaceous biomass that can be used as biofuel; however, its high ash, potassium, sulfur and chlorine content may cause problems when combusted. Napier grass was submitted to vapothermal carbonization (VTC) and hydrothermal carbonization (HTC) processes at 190 and 220 °C to compare their ability to enhance its fuel properties. The different water distribution between phases in the two processes was verified: up to 14.5% of the water vaporized to steam in the VTC ran at 220 °C, while over 99% of the water remained in the liquid state and in contact with the solids during all HTC runs. Both processes improved the calorific value of the Napier grass (up to 20.6% for VTC220 and up to 29.8% for HTC220) due to the higher C content in the chars. Both processes reduced the sulfur content, removing up to 15.3% of it with VTC190 and 28.5% of it with HTC190 compared to that of Napier grass. In contrast, the two processes had different effects on the ash and chlorine content. While HTC removed both ash and Cl from the Napier grass, VTC concentrated it in the chars (ash: 5.6%wt. Napier grass, 3.3%wt. HTC chars, 7.1%wt. VTC; chlorine: 1.08%wt. Napier grass, 0.19%wt. HTC chars, 1.24%wt. VTC). Only the HTC process leached high percentages of Cl (up to 80%), S (up to 70%), sodium (Na, up to 80%) and potassium (K, up to 90%) into the process water. This may prevent fouling and slagging problems when burning HTC char. The biofuel qualities of the raw Napier grass, VTC, and HTC chars were evaluated using two standards: the international standard for solid biofuels, EN ISO 17225, and the Korean regulation for biomass solid recovered fuels (Bio-SRF). Napier grass and VTC chars presented problems regarding Cl content thresholds for both EN ISO 17225 and Bio-SRF. Both VTC and HTC chars along with the Napier grass fulfilled the requirements for heavy metals (Pb, Ni, Cr, and Cd) except for copper. The choice of process in practical applications will depend on the goal; HTC improves fuel quality and VTC has higher high solid, carbon and energy yields.

In situ activation synthesis of tire-derived sorbents for efficient immobilization of elemental mercury from flue gas

Mercury removal from coal combustion flue gas remains a daunting challenge because of the lack of cost-effective sorbents. In this study, the in situ activation synthesis of tire chars was realized through SO2 induction and the tire-derived sorbents were used for elemental mercury (Hg0) removal from the simulated flue gas. Therein the sulfur species in tire chars are regulated. The results indicated that the specific surface area of tire chars was slightly decreased whereas more micropores were generated after SO2 activation. Compared with raw tire char, the sulfur content of tire-derived sorbents was obviously increased. The tire-derived sorbents also contained more sulfur- and oxygen-containing functional groups. For this reason, the Hg0 removal performance of tire-derived sorbents was dramatically increased after SO2 activation. The optimum pyrolysis temperature for the synthesis of tire-derived sorbents was 600 °C. The SO2 concentration in activation atmosphere had little effect on the Hg0 removal performance of tire-derived sorbents. The presence of SO2, NO and O2 was beneficial for Hg0 removal·H2O had little effect on Hg0 removal. The Hg0 adsorption capacity of tire-derived sorbents was further compared with the previously reported sorbents through adsorption dynamic simulations. Furthermore, the mechanism of Hg0 removal over tire-derived sorbents was revealed through XPS analysis and mercury temperature programmed desorption. It was found that the Hg0 removal process was mainly dominated by chemisorption, where organic sulfur species, CO group and COOH/C(O)–O–C group served as active sites for Hg0 capture.

Exploring the Potential of Biomass Pyrolysis for Renewable and Sustainable Energy Production: A Comparative Study of Corn Cob, Vine Rod, and Sunflower

The paper investigates the potential of biomass pyrolysis as a sustainable and renewable energy solution. The study focuses on three biomass types: corn cob, vine rod, and sunflower, which are abundant agricultural residues with potential for biofuel production. The pyrolytic gas, oil, and char produced during pyrolysis at a heating rate of 10 °C/min were analyzed. At the pyrolysis temperature of 500 °C, the corn cob showed the smallest final residual mass of 24%, while the vine rod exhibited the largest mass loss of 40%. Gas analysis revealed the concentrations of CO2, CO, H2, and CH4 in the pyrolytic gas, indicating its energy potential. Sunflower presented the largest calorific value of the produced biogas, while corn cob was the lowest. The chemical composition of the bio-oils was determined, with aliphatic acids identified as the dominant compounds, suggesting their potential for biodiesel production. Fourier Transform–Infrared Spectroscopy (FT-IR) analysis of raw biomass and char products demonstrated varying extents of decomposition among the biomass samples. A multicriteria assessment approach was employed to evaluate the differences between the selected three biomass feedstock and determined that sunflower biomass ranked the highest among the three, although the overall difference was small, confirming the suitability of all three biomass samples for pyrolysis conversion to higher-value-added fuels.

Mercury removal from coal combustion flue gas by mechanochemically sulfur modified straw coke and its mercury stability

This work uses widely sourced rice straw as raw material, sulfur containing substances as modifiers, and mechanochemistry as modification methods to prepare the mechanochemical sulfur modified rice straw char mercury removal adsorbent (S-SC). The influence of modifiers, flue gas components, and the environmental stability of mercury removal products were systematically studied. The mechanochemical sulfur modification (elemental sulfur (ES), Na2S, NaHS) can improve the mercury removal performance of raw rice straw char (R-SC). It enhances mercury adsorption and capture. The ES is the best sulfur specie whose mercury removal rate firstly increases and then decreases as the amount of sulfur added increases. Sulfur modification promotes mercury forms convert to HgS (red) or even HgSO4 with higher thermal stability. The thiophene/elemental sulfur are the main sulfur species for promoting mercury removal. SO2 and NO inhibit mercury removal by ES-SC, while HCl has a promoting effect. As their concentration in the flue gas increases, the proportion of mercury removed by adsorption increases, and the adsorbed mercury transforms into a more thermally stable mercury form. The mercury forms of the spent ES-SC are mainly oxidized and residual form with TCLP leaching rate of zero, which has good environmental leaching stability.

Effect of Fenton pre-oxidation on the physicochemical properties of sludge-based biochar and its adsorption mechanisms for ammonia nitrogen removal

Fenton pre-oxidation, as a promising technology for sludge deep dehydration, has been used intensively; however, the outputs (i.e., low-water-content sludge cakes) need to be further disposed for a full line sludge resource utilization. Carbonization presents a promising approach for disposing of the sludge cake within the process. Here, the physicochemical properties of sludge-based char obtained after Fenton pre-oxidation were studied. Both Fenton pre-oxidized sludge-based char (FSC) and raw sludge-based char (RSC) were produced within the temperature range of 400–600 ℃, and the adsorption performance of the prepared chars, exemplified by their ability to adsorb ammonia nitrogen (NH4+), was tested under various conditions. FSC exhibited superior char yield and adsorption performance compared to RSC, with chemical adsorption being the primary controlling factor. The optimum conditions for FSC were observed at 400 ℃, resulting in a char yield of 72.2 %, and an adsorption capacity of 221.7 mg/g. Notably, FSC demonstrated an increase in C-C, C-N, OC-O, C-O and CC functional groups in comparison to RSC, which suggests that pre-oxidation increases organic matter decomposition and chemical reactivity of the sludge. The introduction of Si-O-Si, Si-O-C and Fe-O-H functional groups in the FSC facilitated ion exchange with NH4+ in an aqueous solution. The key findings indicate that Fenton pre-oxidation not only enhances the adsorption performance of FSC but also reduces the required carbonization temperature for excellent-char preparation. These results demonstrated the potential to integrate sludge deep dewatering, including pre-oxidation, with char preparation.

Co-Gasification Performance of Low-Quality Lignite with Woody Wastes Using Greenhouse Gas CO2—A TG–MS Study

The carbon dioxide gasification performance of low-quality lignite-agroindustrial/forest waste blends was investigated in terms of reactivity, conversion, cold gas efficiency, product gas composition and heating value. The experiments were conducted in a fixed bed unit and a thermal analysis mass spectrometer system. Raw materials, chars, liquids and gases were quantitatively analyzed and their energy content was determined. Synergetic effects and the role of minerals were examined, the latter through chemical and fusibility analyses of the ashes. Ahlada lignite (AL) was of low quality, with a calorific value of 8.9 MJ/kg. The biomass materials, ginning cotton waste (GCW) and pine needles (PN) had calorific values 16.6 MJ/kg and 20.1 MJ/kg, respectively. The slagging/fouling propensity of AL ash was low, whereas that of biomass wastes was medium to high. Thermal treatment of the samples and their blends prior to gasification produced upgraded fuels. A Boudourd reaction occurred above 750 °C. Gasification reactivity followed the order: GCW > PN > AL. AL/PN mixtures presented additivity effects; however, AL/GCW mixtures presented synergy effects. When the lignite was blended with the biochars studied, its conversion increased from 90% to 94.5% and its cold gas efficiency from 31.8% to 35%. Generated gas attained a heating value of about 12 MJ/m3.

Valorisation of spent tire rubber as carbon adsorbents for Pb(II) and W(VI) in the framework of a Circular Economy

Spent tire rubber-derived chars and their corresponding H3PO4 and CO2-activated chars were used as adsorbents in the recovery of Pb(II) ion and (W(VI)) oxyanion from synthetic solutions. The developed chars (both raw and activated) were thoroughly characterized to have insight about their textural and surface chemistry properties. H3PO4-activated chars presented lower surface areas than the raw chars and an acidic surface chemistry which affected the performance of these samples as they showed the lowest removals of the metallic ions. On the other hand, CO2-activated chars presented increased surface areas and increased mineral content compared to the raw chars, having presented higher uptake capacities for both Pb(II) (103–116 mg/g) and W(VI) (27–31 mg/g) ions. Cation exchange with Ca, Mg and Zn ions was appointed as a mechanism for Pb removal, as well as surface precipitation in the form of hydrocerussite (Pb3(CO3)2(OH)2). W(VI) adsorption might have been ruled by strong electrostatic attractions between the negatively charged tungstate species and the highly positively charged carbons’ surface.The results shown in this work allow concluding that the valorisation of spent tire rubber through pyrolysis and the subsequent activation of the obtained chars is an alternative and a feasible option to generate adsorbent materials with a high uptake capacity of critical metallic elements.

Production of Low-Mercury Solid Fuel by Mild Pyrolysis Process

Mercury is considered one of the most harmful ecotoxic elements. A main source of its anthropogenic emissions is fuel combustion. For fuels with a high mercury content, costly methods are required to remove mercury from the flue gases. The solution to this problem is to remove mercury from the fuel before combustion. This can be achieved by a mild pyrolysis process. Solid fuel samples with relatively high mercury content were examined. These included waste (refuse-derived fuel, paper, sewage sludge, and rubber), waste wood biomass (hornbeam leaves, pine and spruce bark), and six coal. The mild pyrolysis process was performed at 300 °C in an argon flow of 500 cm3/min. The residence time was 30 min. Proximate and ultimate analysis (including mercury content) was conducted for raw fuels and chars. The process allowed a significant reduction in mercury content from 36 to 97%. Mercury was most easily removed from biomass and waste with the most difficult being from coal. The effectiveness of mercury removal was determined by the type of fuel and its mercury content. The mercury content in the obtained chars was 0.05–3.4 µg Hg/MJ. The use of such chars will meet current EU emission standards and those to be introduced in the future.

Catalytic performance of activated lignite chars on biomass tar cracking

The tar problems are the major obstacle to developing the biomass pyrolysis technology. The coal chars derived from in situ pyrolysis and/or partially gasification are a promising alternative tar cracking catalyst with great industrial application potential because of its cheap and easily available characteristics. This work investigated the application of lignite chars as catalysts for biomass tar decomposition. Raw lignite char was further gasified with CO2 for 5min (GC5) and 15min (GC15) and used as tar cracking catalysts. Effects of pyrolysis temperature, char/biomass mass ratio, and pore structure of char on the pyrolysis tar removal were studied. The results showed that increasing pyrolysis temperature and char/biomass mass ratio would promote tar decomposition. When using GC15 as catalyst, tar yield was as low as 0.10 wt% at the temperature of 850°C and the mass ratio of 2. Gasification treatment increased the specific surface area of raw char from 284.1 to 342.7 m2/g (GC5) and 435.6 m2/g (GC15). Comparing the catalytic activity of lignite chars with commercial activated carbon demonstrated that mesopores were more influential than micropores in tar removal. In addition, water produced during biomass pyrolysis could in situ contribute to tar reforming and char gasification reactions. The results obtained in this study suggested that a cheaper coal char-based catalyst with excellent performance for biomass tar cracking could be achieved by combining with a coal gasification process and optimizing gasification conditions.

Investigation on the influence of inherent AAEMs on gasification reactivity of solid digestate char

Char reactivity usually determines the overall efficiency of the entire gasification process, while the presence of the alkali and alkaline earth metals (AAEMs) has a catalytic effect on char gasification. In this study, the influence of inherent AAEMs in the gasification behaviour of char was investigated. The char sample was prepared through the pyrolysis of solid digestate derived from anaerobic co-digestion of silage and dairy cattle slurry. The raw char and HCl-washed char were characterized by elemental analyzer, ICP-OES, SEM and XRD to explore their structural changes. HCl-char loses weight in the temperature range of 440–620 °C, and the weight loss percentage is significantly higher than that of char. Ash content of char is reduced by half after a pickling process. AAEMs are largely removed after char acid pickling, resulting in an increase in activation energy of the gasification reaction and a decrease in gasification reactivity, resulting in the gasification reaction time of HCl-char longer than char. Water-soluble AAEM and ion-exchange AAEM affect the evolution of carbon structure, which directly lead to char reactivity during the gasification reaction. As the carbon is consumed, the carbon microcrystalline structure of the residual carbon tends to be ordered, resulting in fewer active free carbon sites for the gasification reaction. Kinetic analysis showed that the loss and deactivation of AAEMs after char acid washing increased the average activation energy Ea by 115.76 KJ/mol compared with the original char.

Improved Nitrogen Oxide Removal from Simulated Flue Gas by Modified Peanut Shell Chars Through Acid Pickling and Nitrogen Doping

Peanut shell char with high alkali metal and ash content was used in this study to remove nitrogen oxide (NO) from simulated flue gases. Effects of acid pickling and nitrogen doping of the biochar (BC) materials on the removal selectivity were investigated in a fixed bed reactor. Results show that CaO, MgO, SiO2, AgO2, CuO, and so on contained in the ash of peanut shell are not conducive to the pore development of biochar and grafting of nitrogen-containing functional groups during the nitrogen doping process. Ash pickling improves the development of pore structure, and decreases the ratios of H/C, O/C, and (O+H)/C. The NO ratio and reaction selectivity of biochar follow the order as pickling treatment (BC-A) > raw peanut shell char (BC) > nitrogen doping treatment (BC-N). Through a combined effect of ash pickling and nitrogen doping, BC-A-N has the highest NO removal ratio and reaction selectivity because of the improved pore characteristics and introduction of nitrogen-containing functional groups.

Effect of nitriding treatment on char reducing nitric oxide at high temperature

To reduce nitric oxide (NO) emissions from coal-fired industrial boilers, char waste could be collected from the tail flue and fed into the furnace to reduce NO, which would also decrease the incomplete combustion loss. Nitriding treatment could be used to enhance the NO reducibility of char waste. In this paper, char with nitriding treatment (nitriding char) was prepared from Shenhua char and urea. The effect of nitriding treatment on char reducing NO at high temperatures (700 °C–900 °C) was studied using a fixed-bed experimental system and various urea masses and pretreatment times. Increasing the urea mass and decreasing the pretreatment time resulted in more urea residue being present in the char, which increased the nitrogen complex which existed in the form of C(N) and caused the surface enrichment of nitrogen element, but blocked the pore structure. In an inert atmosphere, the NO reduction rates of all the nitriding chars were higher than that of the raw char, but there was an optimal limit parameter for the urea mass and pretreatment time. The presence of 2 vol% O2 was not conducive to the NO reduction by nitriding char because of the higher char-nitrogen (char-N) content resulting from the nitriding treatment, which generated more NO and offset the benefit of the nitriding treatment. This paper provides a useful NO control strategy in coal-fired industrial boilers, and the relevant process route has achieved a 20%–35% decrease in NO emissions in engineering applications.

Release of nitrogen during thermochemical conversion of Shenhua bituminous coal under Ar, CO2, and air atmospheres

AbstractCoal thermochemical conversion processes unavoidably generate gaseous pollutants, endangering the environment or influencing synthetic processes downstream. In order to display the differences in release behaviours of nitrogen among different coal thermochemical conversion stages, the nitrogen release characteristics of Shenhua bituminous coal under Ar, CO2, and air atmospheres were investigated using X‐ray photoelectron spectrum (XPS) and thermogravimetry‐mass spectrometry (TG‐MS). Results indicate that the reaction atmosphere has an important influence on nitrogen release. The total released mass of nitrogen when using 100 g raw coal in the whole experiment under Ar, CO2, and air atmospheres is 0.54, 0.64, and 0.75 g, respectively. The organic forms of nitrogen in raw coal and coal char are pyridine nitrogen (N‐6), pyrrole nitrogen (N‐5), quaternary nitrogen (N‐Q), and nitrogen oxide (N‐X). While in the coal ash, the sub‐peaks of N‐Q and N‐X disappear entirely, leaving only N‐5 and N‐6 sub‐peaks. The released nitrogen‐containing gas consists of NH3, HCN, NO, and NO2 during experiments in CO2 and air atmospheres. However, only NH3 and HCN are detected during experiments in the Ar atmosphere. The revolution characteristics of NH3 and HCN under Ar and CO2 atmospheres are similar.

Reactivity Effects of Inorganic Content in Biomass Gasification: A Review

This review article discusses the effects of inorganic content and mechanisms on raw biomass and char during gasification. The impacts of the inherent inorganics and externally added inorganic compounds are summarized based on a literature search from the most recent 40 years. The TGA and larger-scale studies involving K-, Ca-, and Si-related mechanisms are critically reviewed with the aim of understanding the reaction mechanisms and kinetics. Differences between the reaction pathways of inorganic matter, and subsequent effects on the reactivity during gasification, are discussed. The present results illustrate the complexity of ash transformation phenomena, which have a strong impact on the design of gasifiers as well as further operation and process control. The impregnation and mixing of catalytic compounds into raw biomass are emphasized as a potential solution to avoid reactivity-related operational challenges during steam and CO2 gasification. This review clearly identifies a gap in experimental knowledge at the micro and macro levels in the advanced modelling of inorganics transformation with respect to gasification reactivity.

Transformation and fate of sulphur during steam gasification of a spent tyre pyrolysis char

The transformation of sulphur (S) during steam gasification of a spent tyre pyrolysis char (STPC) was investigated by tracing the evolution of S species and their mass fractions through X-ray photoelectron spectroscopy analysis. The raw pyrolysis char and demineralised char samples were respectively reacted with steam in a vertical fixed bed reactor over a range of temperature (850, 950, 1050 °C), steam concentration (33.3, 50.0, 66.7 vol% steam in N2) and gasification time (0.5, 1, 2, 3, 4 h). The mass fraction of S in the partially gasified char increased with increasing time at 850 °C and 950 °C, but decreased at 1050 °C. However, the net amount of S retained in the gasified char relative to that in the raw STPC decreased with increasing mass loss ratio, implying that S loss was faster than carbon consumption. The dominant S species in the pyrolysis char were aliphatic sulphide and ZnS. After steam gasification, more than 80% S species in the gasified chars were in the form of organic S. The proportion of organic S increased while that of inorganic S decreased with increasing gasification time and temperature, regardless of steam concentration. Thiophene, aliphatic sulphide, sulphone and sulphoxide became the main organic S species while ZnS and sulphate were the dominant inorganic S species. Aliphatic sulphide, sulphone and sulphoxide were converted to more thermally stable thiophene. Sx released from ZnS or COS produced from CaSO4 reacted with the carbon matrix to form sulphone and sulphoxide in the gasified char.

Coupling effect of Fe-based catalyst on Nitrogen oxides control in the process of nitrogen reduction and combustion denitration of long flame coal pyrolysis

ABSTRACT Civil dispersed coal combustion has become an important source of Nitrogen oxides (NOx), which has caused serious pollution to the ecological environment. In order to control NOx emission in the combustion process of civil coal, coal-based solid clean fuel should be used instead of dispersed combustion of coal, so as to achieve the purpose of reducing NOx emission. The pyrolysis and combustion tests of different iron additives loaded coals were performed. The raw and pyrolytic chars were prepared and characterized by X-ray photoelectron spectroscopy (XPS), nitrogen adsorption, scanning electron microscope (SEM) and X-ray diffraction (XRD). The results indicate that iron additives introduced into raw coal in one step have coupling effect on NOx emission control during pyrolysis and combustion. The addition of iron can lead to more Fe2O3, Fe3O4 and α-Fe in coke and promote coke cracking. Supporting iron catalysts could make coke structure more porous, which increases the contact area of gas. These all make the conversion of N2 increase from 16.71% to 29.64% during pyrolysis. The existence of iron catalyst can also promote the proportion of pyridinic N (N-6) and quaternary nitrogen (N-Q) relatively increase. At the same time, the existence of iron catalyst is beneficial to catalytic reduction of NOx by C and CO. The emissions of NOx during combustion can be reduced by 34.01%. The iron catalyst introduced in one step has a coupling effect on NOx control in coal pyrolysis-combustion process, which realizes a two-step nitrogen reduction effect in combustion. It provides theoretical basis for ultra-low NOx emission in clean fuel combustion.

Online characterization of pyrolysis products and kinetics study for the pyrolysis of a coal

The compositional distribution of pyrolysis products is related to the molecular structure of coal and pyrolysis parameters. In this study, gaseous products generated from the pyrolysis of two low-rank coals were analyzed by an online home-built infrared detection system. The effect of heating rate and temperature on compositional distribution was considered and evaluated. Fourier transform infrared (FTIR), gas chromatograph/mass spectrometry (GC/MS), and Orbitrap-MS were employed to analyze other pyrolysis products such as raw coals, chars, and tars. In the pyrolysis process, oxygen-containing compounds in coal were the first species to participate in pyrolysis reactions. With the enhancement of temperature, the content of aromatic hydrocarbons showed an increasing trend, and the contents of aliphatic hydrocarbons and oxygenates decreased. In the four major pyrolysis gases, the yield of H2 was the highest and the lowest for CO2. In addition, dynamic curves of the main pyrolysis gas were obtained, and the activation energies of pyrolysis gases were calculated by Ozawa-Flynn-Wall’s (OFW) method. The possible generation pathways of gaseous products were proposed.

Catalytic effects of inherent AAEM on char gasification: A mechanism study using in-situ Raman

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 R0.5 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.