Char structure characterised by Raman spectroscopy and its correlations with combustion reactivity

Raman spectroscopy was applied to characterise the microstructure of coal chars generated under various heat treatment conditions, which was correlated with the combustion reactivity measured by thermogravimetric analysis. The Raman spectra were fitted with the combination of 4 Lorentzian bands and 1 Gaussian band. It was found that the increase of char microstructural order under heat treatment can be characterised by Raman parameters, in particular the band area ratios, indicated by the increase in I_G/I_All and the decrease in I_D1/I_G, I_D2/I_G, I_D3/I_G and I_D4/I_G with increasing treatment temperature and/or time. The combustion reactivity of the chars from demineralised coals was found to have good correlations with the band area ratios, independent of coal type and heat treatment condition. It was found that the presence of inorganic matter in coal chars marginally affected the evolution of the average char microstructure. However, it did affect the char reactivity evolution. It was confirmed that the thermal deactivation of coal char during heat treatment was dependent not only on the ordering of char crystalline structure but also on the loss of catalytic activity of the inorganic matter.     

In-bed char combustion of Australian coals in PFBC. 2. Char combustion without secondary fragmentation

Char combustion parameters that significantly affect the in-bed combustion of char in PFBC were determined experimentally using a batch-fed PFBC. The ratio of carbon to oxygen consumed on the surface of a burning char particle was determined and it was concluded that CO was the only product of char combustion in PFBC.

Model simulations revealed that, for PFBC, mass transfer controlled the combustion of large char particles ≥2 mm, whereas the combustion of small char particles below 0.9–2 mm was controlled by both mass transfer and chemical kinetics.

System pressure influenced the char combustion via the interaction between chemical kinetics and the mass transfer of oxygen to the char. Char particle temperature varied markedly with oxygen partial pressure in the particulate phase, indicating a distribution of char particle combustion rates in PFBC. In modelling char combustion in PFBC, the temperature of char particles in the bed should be calculated at different locations based on a heat balance around the burning char particle taking into account the local bed oxygen concentration.     

Reactivity and structural change of coal char during steam gasification

This study is intended to clarify the relationship among the reactivity of coal char with steam, structural change in residual carbon, and ash behavior. Steam gasification of various coal chars and demineralized chars was carried out in a fixed-bed reactor. After gasification, the reacted char was analyzed using laser raman spectroscope (LRS), and scanning electron microscope, energy dispersive X-ray spectroscope (SEM/EDX) mapping. Results of SEM images and EDX-mappings revealed that novel parallel analysis of cross correlation between EDX-mapping and LRS-mapping was found to be very effective for the comprehensive evaluation of ash behavior and carbonaceous structure. As the gasification reaction proceeds, the reactivity of the char was varied; existence of Si and Al seemed to suffocate the char reactivity.     

Effect of pyrolysis pressure and heating rate on radiata pine char structure and apparent gasification reactivity

The knowledge of biomass char gasification kinetics has considerable importance in the design of advanced biomass gasifiers, some of which operate at high pressure. The char gasification kinetics themselves are influenced by char structure. In this study, the effects of pyrolysis pressure and heating rate on the char structure were investigated using scanning electron microscopy (SEM) analysis, digital cinematography, and surface area analysis. Char samples were prepared at pressures between 1 and 20 bar, temperatures ranging from 800 to 1000 °C, and heating rates between 20 and 500 °C/s. Our results indicate that pyrolysis conditions have a notable impact on the biomass char morphology. Pyrolysis pressure, in particular, was found to influence the size and the shape of char particles while high heating rates led to plastic deformation of particles (i.e. melting) resulting in smooth surfaces and large cavities. The global gasification reactivities of char samples were also determined using thermogravimetric analysis (TGA) technique. Char reactivities were found to increase with increasing pyrolysis heating rates and decreasing pyrolysis pressure.     

Structural ordering of coal char during heat treatment and its impact on reactivity

The effect of heat treatment on the structure of an Australian semi-anthracite char was studied in detail in the 850-1150°C temperature range using XRD, HRTEM, and electrical resistivity techniques. It was found that the carbon crystallite size in the char does not change significantly during heat treatment in the temperature range studied, for both the raw coal and its ash-free derivative obtained by acid treatment. However, the fraction of the organized carbon in the raw coal chars, determined by XRD, increased with increase of heat treatment time and temperature, while that for the ash-free coal chars remained almost unchanged. This suggests the occurrence of catalytic ordering during heat treatment, supported by the observation that the electrical resistivity of the raw coal chars decreased with heat treatment, while that of the ash-free coal chars did not vary significantly. Further confirmatory evidence was provided by high resolution transmission electron micrographs depicting well-organized carbon layers surrounding iron particles. It is also found that the fraction of organized carbon does not reach unity, but attains an apparent equilibrium value that increases with increase in temperature, providing an apparent heat of ordering of 71.7 kJ mol⁻¹ in the temperature range studied. Good temperature-independent correlation was found between the electrical resistivity and the organized carbon fraction, indicating that electrical resistivity is indeed structure sensitive. Good correlation was also found between the electrical resistivity and the reactivity of coal char. All these results strongly suggest that the thermal deactivation is the result of a crystallite-perfecting process, which is effectively catalyzed by the inorganic matter in the coal char. Based on kinetic interpretation of the data it is concluded that the process is diffusion controlled, most likely involving transport of iron in the inter-crystallite nanospaces in the temperature range studied. The activation energy of this transport process is found to be very low, at about 11.8 kJ mol⁻¹, which is corroborated by model-free correlation of the temporal variation of organized carbon fraction as well as electrical resistivity data using the superposition method, and is suggestive of surface transport of iron.     

The influence of high-temperature crystallite growth and petrography of pulverized char on combustion characteristics

In this paper, Yangquan anthracite was separated into three different coal lithotypes in terms of density. The effect of high-temperature crystallite growth on char combustion of coal is characterized. It shows that there is large difference between the combustion characteristics of the two lithotypes of coal (one is <1.55 g/ml of density and the other is 1.55-1.855 g/ml), and that the development of structural ordering decrease the combustion rate to a certain degree. The precise method of using thermogravimetry analyser to study the kinetics of char combustion reaction is also discussed. Besides, a feasible measure to process the experimental data is introduced.     

The physical character of coal char formed during rapid pyrolysis at high pressure

Rapid pyrolysis was conducted in a drop tube reactor using seven coals under various operating conditions. In addition to dense char, porous chars (network char and cenospheric char) were formed by the rapid pyrolysis under certain conditions. Porous char was mainly composed of film-like carbon and skeleton carbon. The pyrolyzed coal char particles were characterized in detail. Morphology and bulk density of porous char were quite different from the dense char formed under the same conditions, but elemental composition and BET surface area were similar to each other. CO₂ gasification reactivity of porous char was lower than dense char in the later gasification stage, and this was ascribed to the low reactivity of skeleton carbon.     

Composition and morphology of char particles of fly ashes from industrial burning of high-ash coals with different reactivity

A comparative investigation of the composition and the morphology of char particles was conducted: char particles were recovered from fly ashes of two power stations in Russia from burning of high- and low-reactivity high-ash coals; the known results of studies of char particles generated in laboratory conditions from coals characterized according to the ASTM D388-98a standard were also used. The composition of organic and mineral components of different fraction char particles was studied. An inverse correlation between the content of the organic substance and the iron content in char particles was identified. The morphology of the char particles for the three main types (Cenospheric, Network and Solid) and the influence of coal reactivity and temperature on char morphology were investigated. The morphology of the mineral component of char particles of the two varieties of coals was also studied. It was shown that the high-temperature of industrial burning of Ekibastuz coal results in melting of the mineral substance and forming of micron-scale microspheres located in the lamellar porous structure of the carbon matrix.     

Fe2O3对高变质程度脱灰煤热解反应性与半焦结构的影响

利用热天平研究了共混合法负载Fe₂O₃高变质程度脱灰煤的热解反应性,结果表明煤粉负载Fe₂O₃后热解反应性高于无负载的热解反应性。负载Fe₂O₃煤样在程序升温加热的马弗炉中制备出半焦,利用FTIR、XRD和RAMAN 等分析了半焦结构。由TG和FTIR可知,负载Fe₂O₃煤样热解时,热解转化率增加,热解后自由基增加。由XRD可知,Fe₂O₃没有使得煤样半焦的002峰衍射角发生明显变化,但使L_a和L_c参数明显降低,说明半焦的微晶结构石墨化程度降低。另外,在XRD分析谱图中发现部分Fe₂O₃被还原成FeO。由RAMAN可知,Fe₂O₃使半焦的G峰峰面积降低,D峰峰面积增加,说明半焦的有机结构有序化程度降低。     

Modeling the influence of changes in aliphatic structure on char surface area during coal pyrolysis

The influence of changes in aliphatic structure on char surface area during coal pyrolysis was modeled, and the effect was introduced to a previous char surface area model for lignite pyrolysis established based on the chemical percolation devolatilization (CPD) model. The modified model can predict not only the N₂ and CO₂ char surface area during rapid pyrolysis of three lignites but also the CO₂ char surface area of two high-volatile bituminous coals; the agreement of the modified model with experiments is improved at high temperatures. The decrease in aliphatic chain length can reduce adsorption positions around aromatic core, and decrease char surface area. When mass release is more than 55% at about 1,100 K, the predicted N₂ char surface area starts to decrease with further generation of volatiles, and the increase of predicted CO₂ char surface area with increasing generation of volatiles also become slow at the end of mass release.     

Catalytic effect of Na–Fe on NO–char reaction and NO emission during coal char combustion

The catalytic reduction of NO over coal-derived chars and the catalytic effect of Na–Fe on NO emission during char combustion were investigated in a quartz fixed bed reactor. The catalytic characteristics of Na and Fe in the NO–char reaction were studied and compared in detail. The results show that the catalytic activity of Na depends greatly on its loading amount, while the activity of Fe is more sensitive to temperature. Na–Fe composite catalysts were also prepared with chars as support. Synergistic effect was found both in the reduction of NO and the char combustion. The Na–Fe composite catalysts exhibit significantly higher catalytic activity than the mono-metallic catalysts with the same metal loading amount. It is intriguing to note that the effectiveness of the catalysts on reducing NO emission during char combustion is in the same order as that in the NO–char reaction, i.e. the chars with catalysts not only have high activity in NO–char reaction but also emit less NO during their combustion.     

Effect of pyrolysis temperature on the char micro-structure and reactivity of NO reduction

A phenol-formaldehyde resin (PFR) and a bituminous coal (SH) were pyrolyzed at various temperatures. The structure and the char-NO reactivity were analyzed in order to examine the effect of pyrolysis temperature on the micro-structure of the resulting char and further on the reactivity towards NO. Micro-structure of the char samples was characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and Raman spectroscopy. It was indicated that the micro-structure of PFR char and coal char experienced remarkable changes during pyrolysis, which resulted in the decrease of phenolic OH, aromatic hydrogen and more ordered structure. The pyrolysis temperature showed a weak impact on the reactivity of PFR char but comparatively remarkable impact on that of coal char at lower reaction temperature. Mineral matter in coal char presented a weak effect on the reactivity. This paper was presented at the 7 ^th China-Korea Workshop on Clean Energy Technology held at Taiyuan, China, June 26–28, 2008.     

Influence of pyrolysis conditions on the structure and gasification reactivity of biomass chars

The physical and chemical structure as well as gasification reactivities of chars generated from several biomass species (i.e. pinus radiata, eucalyptus maculata and sugar cane bagasse) were studied to gain insight into the role of heating rate and pressure on the gasification characteristics of biomass chars. Char samples were generated in a suite of reactors including a wire mesh reactor, a tubular reactor, and a drop tube furnace. Scanning electron microscopy analysis, X-ray diffractometry, digital cinematography and surface area analysis were employed to determine the impact of operating conditions on the char structure. The global gasification reactivities of char samples were also determined for a range of pressures between 1 and 20 bar using pressurised thermogravimetric analysis technique. Char reactivities were found to increase with increasing pyrolysis heating rates and decreasing pyrolysis pressure. It was found that under high heating rates the char particles underwent plastic deformation (i.e. melted) developing a structure different to that of the virgin biomass. Pressure was also found to influence the physical and chemical structures of char particles. The difference in the gasification reactivities of biomass chars at pressure was found to correlate well with the effect of pyrolysis pressure on the graphitisation process in the biomass char structure.     

A comparative reactivity and kinetic study on the combustion of coal-biomass char blends

The combustion behavior and kinetics of various biomass chars, a lignite and a hard coal char and their blends were investigated. Pure fuel chars were compared to blended chars with respect to their performance during combustion. Non-isothermal thermogravimetry experiments were performed in air atmosphere, over a temperature range of 25-850 °C and at a heating rate of 10 °C/min. Kinetic evaluation was performed using a power law model. Reaction kinetic parameters were obtained by modeling the combustion of biomass and coal chars as a single reaction, with the exception of lignite and olive kernel chars, the combustion of which was modeled by two partial reactions. A single reaction model was used in the case of coal-wood char blends, while for the lignite-biomass char blends two partial reactions were used. Reactivity was assessed using the specific reaction rate, as a function of conversion. Biomass chars were generally more reactive than those of hard coal and lignite. The combustion behavior of the blends was greatly influenced by the rank of each coal (hard coal or lignite) and the proportion of each component in the blend. Combustion performance of the blends showed some deviation from the expected weighted average of the constituent chars. An attempt was made to estimate the kinetics of the blends using, as a basis, the parameters estimated for the individual components. In this case, because of the interactions between the components of the blends, the kinetic parameters needed to be slightly modified. Alteration in reactivity was more pronounced in the case of lignite-biomass chars than coal-wood chars.     

Fe2O3对高变质程度脱灰煤热解反应性与半焦结构的影响

利用热天平研究了共混合法负载Fe₂O₃高变质程度脱灰煤的热解反应性，结果表明煤粉负载Fe₂O₃后热解反应性高于无负载的热解反应性。负载Fe₂O₃煤样在程序升温加热的马弗炉中制备出半焦，利用FTIR、XRD和RAMAN 等分析了半焦结构。由TG和FTIR可知，负载Fe₂O₃煤样热解时，热解转化率增加，热解后自由基增加。由XRD可知，Fe₂O₃没有使得煤样半焦的002峰衍射角发生明显变化，但使L_a和L_c参数明显降低，说明半焦的微晶结构石墨化程度降低。另外，在XRD分析谱图中发现部分Fe₂O₃被还原成FeO。由RAMAN可知，Fe₂O₃使半焦的G峰峰面积降低，D峰峰面积增加，说明半焦的有机结构有序化程度降低。     

Significance of char active surface area for appraising the reactivity of low- and high-temperature chars

Contemporary char reactivity studies have focussed primarily on coal chars prepared under severe (high-temperature) conditions. In this study, the reactivity of chars prepared under mild (low-temperature) conditions has been addressed. A thermogravimetric analysis system (TGA) was used to determine the reactivity of chars in oxidizing atmosphere using isothermal or non-isothermal techniques. Coal chars were prepared in a TGA or in a slow heating rate organic devolatilization reactor (SHRODR) at a temperature range between 500 ° and 950 °C. The chars prepared by mild pyrolysis of coal at 500 °C are shown to be highly reactive. Comparison of reactivities of low- and high-temperature chars shows that the low-temperature chars exhibit higher reactivity than either the parent coals or the high-temperature chars. Correlation between isothermal reactivity results (e.g. time) and non-isothermal reactivity data (e.g. temperature) has been obtained. Hydrogen contents of chars correlate well with the reactivity of the chars. The study confirms the importance of oxygen chemisorption capacity as a significant reactivity parameter for both low- and high-temperature chars. A new approach has been used for calculating the oxygen chemisorption capacity of chars by accounting for the carbon surface sites occupied by hydrogen (and, therefore, these sites were unavailable for oxygen chemisorption). The occupied sites are readily freed during reactivity measurements and thus were available for participation in carbon-oxygen reactions.     

Leaching of ashes and chars for examining transformations of trace elements during coal combustion and pyrolysis

One sub-bituminous coal and two bituminous coals were subjected to the combustion and pyrolysis by slow heating to a temperature ranging 550-1150 °C. Leaching of raw coals, ashes and chars with dilute HCl and HNO₃ was carried out, and leachate concentrations of major and trace elements were determined. Such a comparative leaching method was validated for characterizing the modes of occurrence of trace elements in coal and their transformations upon heating. Leaching results suggested that Be, V, Co, Cr and Ni were partially associated with organic matter, and As was partially associated with pyrite. During the ashing at 550-750 °C, the organically associated trace elements in coal formed some acid-soluble species. After the ashing at 1150 °C, Be, Co, Cr and Ni, together with Mn, Zn, and Pb, were immobilized in ash against leaching, whereas As was not immobilized. After pyrolysis, the organically associated trace elements in chars remained insoluble in both acids, and some HNO₃-soluble As in coal turned to a HNO₃-insoluble species.     

秸秆灰对煤焦气化反应性的影响

钾、钙对煤焦气化反应性具有重要影响,秸秆灰中含有丰富的钾、钙。以神木煤为制焦原料,通过STA409PC同步热分析仪研究了秸秆灰对煤焦气化反应性的影响,并通过测定煤焦的碘吸附值对其比表面积及孔隙结构进行了分析。结果表明：煤与玉米秸秆共焦化所得煤焦的气化反应性明显优于单独煤焦,且与玉米秸秆的添加比例有关;采用脱灰玉米秸秆与煤共焦化所得煤焦的气化反应性与单纯煤焦相近;将与玉米秸秆等效的秸秆灰添加到煤焦中,煤焦的气化效果明显优于等效玉米秸秆与煤共焦化所得煤焦。煤焦碘吸附值测定结果表明,脱灰秸秆与煤共焦化所得煤焦的碘吸附值最大,单纯煤焦的碘吸附值最小,说明玉米秸秆及秸秆灰对煤焦的比表面积及孔隙结构具有重要的影响,与煤焦的气化反应性评价结果基本一致。     

Fly ash and coal char reactivity from Thermo-gravimetric (TGA) experiments

The purpose of this research is to determine the reactivity of a sample of high carbon fly ash obtained from a circulating fluidized bed (CFB) gasification system and benchmark it against three other chars prepared at different pyrolysis temperatures in a laboratory drop tube furnace (DTF).Isothermal and non-isothermal thermo-gravimetric (TGA) experiments were used to determine sample reactivities. Structural analysis tests were carried out to establish the influence of the pore characteristics and Scanning Electron Microscope (SEM) pictures were taken for sample morphology. In-spite of high (BET) surface area and pore volume; reactivity parameters such as activation energy, kinetic rate coefficient, half life, burnout temperature and time proved the fly ash to be the least reactive. The low reactivity is associated with its carbon thermal deactivation. Non-isothermal tests also show the fly ash to be heterogeneous in composition. Of all the samples, the char prepared in the laboratory at the lowest pyrolysis temperature was the most reactive.     

煤焦二氧化碳气化反应活性影响因素研究现状

煤二氧化碳气化反应是一种煤清洁利用的手段,其关键是提高反应活性。综述了原煤性质、热解过程、反应温度与压力、催化剂,以及二氧化碳气速、煤焦的粒度等因素对反应活性的影响,并对煤焦气化技术进行了展望。