Effect of ionic liquids on the microstructure and combustion performance of Shengli lignite.

To ensure the safe transportation and efficient utilisation of lignite, it is important to inhibit its spontaneous combustion. In this study, Shengli lignite (SL+) was used as the research object and ionic liquids (ILs) were used to pretreat the lignite to investigate their effect on the combustion performance of lignite. On this basis, the relationship between the structure and combustion performance of lignite with different structures (heat treatment, oxidation) after ILs treatment was investigated. Results indicated that the combustion of lignite treated with ILs shifted towards higher temperatures. The most pronounced effect was observed in coal samples treated with [BMIM]Cl (1-butyl-3-methylimidazolium chloride), with the maximum combustion rate corresponding to a temperature increase of approximately 57 °C compared to that of the untreated lignite. For the heat-treated lignite, the temperature corresponding to the maximum combustion rate was approximately 38 °C higher than that of the untreated lignite. After [BMIM]Cl treatment, the combustion performance of the heat-treated lignite changed very slightly. In contrast, for oxidised lignite, the temperature corresponding to the maximum combustion rate decreased by approximately 54 °C compared with that of the untreated lignite and increased by approximately 135 °C after treatment with [BMIM]Cl. The characterisation results show that the content of aliphatic hydrogen and oxygen-containing functional groups decreased in the heat-treated lignite, while the content of hydroxyl and carboxyl groups increased in the oxidised lignite. The microstructure of the heat-treated lignite after [BMIM]Cl treatment changed slightly. In contrast, in the oxidised lignite after [BMIM]Cl treatment, the content of hydroxyl and carboxyl groups decreased, whereas the content of ether (C-O-) structures increased. The increased content of ether (C-O-) structures improved the stability of the coal samples. It is believed that the inhibition of lignite combustion is mainly attributed to the high stability of the ether (C-O-) structures. The kinetic analysis demonstrated that the ILs treatment increased the activation energy of lignite combustion.

Effect of Iron Component on the Structural Evolution of Carbon Bonds in Hydrochloric Acid-Demineralized Lignite During Pyrolysis.

The pyrolysis characteristics of hydrochloric acid-demineralized Shengli lignite (SL+) and iron-added lignite (SL+-Fe) were investigated using a fixed-bed reactor. The primary gaseous products (CO2, CO, H2, and CH4) were detected via gas chromatography. Fourier-transform infrared spectroscopy and X-ray photoelectron spectroscopy techniques were used to study the carbon bonding structures of the lignite and char samples. In situ diffuse reflectance infrared Fourier transform spectroscopy was used to better understand the effect of the iron component on the transformation of the carbon bonding structure of lignite. The results showed that CO2 was released first during pyrolysis, followed by CO, H2, and CH4, and this order was unaffected by the addition of the iron component. However, the iron component promoted the generation of CO2, CO (<340 °C), and H2 (<580 °C) at lower temperatures and inhibited the formation of CO and H2 at higher temperatures while also inhibiting the release of CH4 throughout the pyrolysis process. The iron component may form an active complex with C=O and a stable complex with C-O, which can promote the fracture of carboxyl functional groups and inhibit the decomposition of ether bonds, phenolic hydroxyl groups, methoxy groups, and other functional groups, thus promoting the decomposition of aromatic structures. At low temperatures, it promotes the decomposition of aliphatic functional groups and finally the bonding and fracture of functional groups in coal, leading to the change of the carbon skeleton, resulting in the change of gas products. However, it did not significantly affect the evolution of -OH, C=O, C=C, and C-H functional groups. According to the above results, a developing reaction mechanism model of Fe-catalyzed lignite pyrolysis was established. Therefore, it is worth doing this work.

Effect of the Iron Component on Microcrystalline Structure Evolution of Hydrochloric Acid-Demineralized Lignite during the Pyrolysis Process.

Hydrochloric acid-demineralized Shengli lignite (SL+) and iron-added lignite (SL+-Fe) were thermally degraded using a fixed-bed device to better understand the effect of the iron component on the microcrystalline structure transformation properties of lignite during the pyrolysis process. The primary gaseous products (CO2, CO, H2, and CH4) were detected by pyrolysis-gas chromatography. X-ray diffraction and Raman spectra were adopted to analyze the microcrystalline structure of lignite and chars. The results indicated that the iron component had a catalysis effect on the pyrolysis of SL+ below 602.6 °C. The pyrolysis gases released in the order of CO2, CO, H2, and CH4, and the addition of the iron component did not change the sequences. The iron component promoted the generation of CO2, CO, and H2 in the low-temperature stage. During the high-temperature stage, the iron component inhibited the formation of CO and H2. The formation of CH4 was inhibited by the iron component throughout the pyrolysis process. The evolution characteristics of -OH, C=O, C=C, and C-H functional groups were not significantly affected, and the fracture of aliphatic functional groups and C-O functional groups was inhibited by the iron component during the pyrolysis process. The iron component restricted the spatial regular arrangement tendency of aromatic rings and facilitated the decrease in the small-sized aromatic ring but inhibited the formation of large aromatic rings (≥6 rings) and the content decrease in side chains during the pyrolysis process. Notably, the effects of the iron component on the formation of gaseous products were associated with the microstructure evolution of lignite.

Effects of Water-Soluble Sodium Compounds on the Microstructure and Combustion Performance of Shengli Lignite.

Different water-soluble sodium compounds (NaCl, Na2CO3, and NaOH) were used to treat Shengli lignite, and the resulting effects on the microstructure and combustion performance of the coal were investigated. The results showed that Na2CO3 and NaOH had a significant impact on combustion performance of lignite, while NaCl did not. The Na2CO3-treated lignite showed two distinct weight-loss temperature regions, and after NaOH treatment, the main combustion peak of the sample moved to the high temperature. This indicates that both Na2CO3 and NaOH can inhibit the combustion of lignite, with the latter showing a greater effect. The FT-IR/XPS results revealed that Na+ interacted with the oxygen-containing functional groups in lignite to form a "-COONa" structure during the Na2CO3 and NaOH treatments. It is deduced that the inhibitory effect on combustion of lignite may be attributed to the stability of the "-COONa" structure, and the relative amount is directly correlated with the inhibitory effect. The XRD/Raman analysis indicated that the stability of the aromatic structure containing "-COOH" increased with the number of "-COONa" structures formed. Additionally, experiments with carboxyl-containing compounds further demonstrated that the number of oxygen-containing functional groups combined with Na was the main reason for the differences in the combustion performance of treated lignite.

[Coal Combustion Reactivity of Different Metamorphic Degree and Structure Changes of FTIR Analysis in Pyrolysis Process].

The combustion reaction of raw coals in the air was analyzed withThermal Gravimetric Analyzer 6300 and FTIR (Fourier Transform infrared spectroscopy). The raw coals came from three different sources which were SL lignite, SH bitumite and TT anthracite. The chars were prepared by fixed bed pyrolysis equipment in different reaction temperature. The overlapping peaks were fitted into some sub-peaks by Gaussian function. The aromatic index (R), aromatic structure fused index (D) and organic maturity index (C) were calculated through sub-peaks areas. It showed that three kinds of ignition temperature of SL, SH and TT were 299.3, 408.2 and 441.0 ℃ respectively. The peak temperature of maximum weight loss rate were 348.6, 480.5 and 507.0 ℃ respectively. With the increase of coal rank, both ignition temperature and peak temperature of maximum weight loss rate increased in some degree. The result showed that coal structure was very complex. Vibration absorption peaks of hydroxyl (­OH), aliphatic hydrocarbons (­CH2，­CH3), aromatic (CC), oxygen-containing functional group(CO, C­O) and other major functional groups could be observed in the infrared spectral curves of all samples. With the increase of pyrolysis temperature, infrared vibration absorption peaks of aliphatic hydrocarbons (­CH2­, ­CH3) were gradually decreased. the stretching vibration peak of CO which was at 1 700 cm-1 almost disappeared after coked at 550 ℃. SL samples' absorption peak area infrared curve of oxygen functional groups at 1 000～1 800 cm-1 was more complex. With the increase of coking temperature they changed more significantly compared with others. While peak position and peak intensity for aromatic CC absorption peaks of SH and TT did not change apparently when temperature was changing. Variation trends of main functional groups among three ranks of coals were obviously different with changes of R, D and C values.