低阶煤低温干燥工艺及其对煤性质的影响研究
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摘要
针对神华集团内蒙古矿区低阶动力煤水分含量高、挥发分高、发热量低、应用范围窄、不适合远距离运输等特点,研究出高效、快速、自燃爆炸风险低,无尾气污染的低温干燥工艺,将煤的低位发热量提高到20.9MJ/kg以上,增加低阶煤的应用范围和经济附加值。研究干燥对煤中官能团构成、结构、表面结构与形貌、比表面积、表面元素价态、氧化动力学参数等性质的影响,以及这些影响与煤炭的自燃倾向性之间的关系,进而确定水分脱除效果好,自燃倾向性影响低的高含水低阶煤干燥提质的最佳工艺条件。
研究结果表明:当使用热空气为干燥介质对高含水低阶煤进行快速对流干燥时,在热风流量2000L/min的条件下,170℃热空气可在10min内将煤中水分从30%降低至15%以下,煤的低位发热量提升至23.51MJ/kg,而且干燥尾气内没有气体有机污染物,对环境无影响,干燥也不增加煤的煤尘爆炸性;随着热空气温度的提高和干燥时间的延长,煤的脱水效果变好,但当煤中水分过低时,煤样会回吸空气中的水蒸气。FTIR、SEM、TGA、XPS、BET对干燥前后煤样的表征则表明:当热空气超过170℃,干燥时间超过10min时,热空气会氧化低阶煤,导致煤中的桥键和侧链等官能团氧化;表面微观结构渐趋粉化,热应力裂纹和氧化裂隙增加;煤中孔的数量的减少,孔半径增大;煤氧复合活化能迅速降低,使煤更易与氧结合;煤表面碳元素的氧化程度逐渐加剧;这些变化都会导致煤的自燃倾向性增强。
以氮气为干燥介质的实验研究表明:在同等条件下,氮气干燥的效果明显优于空气。对干燥后煤的XPS分析也表明,氮气干燥的煤其表面被氧化的程度大为降低,干燥过程中的煤尘爆炸危险性也低,因此,采用氮气干燥具有安全、节能、环保等优点。但氮气不能低成本无限取用,开发高比例氮气循环的低温干燥工艺,才是解决低阶煤低温干燥提质的根本途径。
Low temperature convective dryness technology of high moisture contently low rank coal was investigated using hot air and nitrogen as the medium. The coal in the experiments was obtained from Shenhua Group Jinfeng Coal Colloery in Inner Mongolia. Characters of the coal are high water content, high volatile, low net calorific value and easily spontaneous combustion. The purpose of this study is to find out optimum conditions of low temperature fast dryness techonology to enhance it’s quality. At the same time, samples of the coal before and after drying were determined by FTIR, SEM, TGA, XPS, and BET to compare the effect of low temperature dryness on the functional group constitute, surface morphology, specific surface area, surface carbon valence states and oxidation kinetic parameters.
Result of the experiments indicates that the fast convective dryness process was carried out under hot air and it is flowed 2000L/min 170℃hot air is reduced the moisture from 30% to less than 15% within the 10min, the net calorific value of the coal was raised to 23.51MJ/kg, and there is no organic pollutants on dyrness exhaust gas and the process didn’t increase risk of coal dust explosion. As the hot air temperature enhanced and the drying time extended, more moisture was removed. The detection result of FTIR, SEM, TGA, XPS and BET indicated that if the hot air exceeded 170℃and drying time was more than 10min, the coal would be oxidized and a series of changes in the coal would happen, such as the bridge bond and lateral chain structure oxidation, surface micro structure was powdered and the oxidation degree of the coal surface carbon was deepened. All these changes will lead to increasing tendency of spontaneous combustion.
Experiment studies of nitrogen as the medium have shown that: the nitrogen dryness effect is better than hot air and the oxidation extents of coal surface has been reduced. However, the nitrogen couldn’t be low-cost unlimited use and development of the high proportion nitrogen cycle low temperature drying technology is the fundamental solution.
研究结果表明:当使用热空气为干燥介质对高含水低阶煤进行快速对流干燥时,在热风流量2000L/min的条件下,170℃热空气可在10min内将煤中水分从30%降低至15%以下,煤的低位发热量提升至23.51MJ/kg,而且干燥尾气内没有气体有机污染物,对环境无影响,干燥也不增加煤的煤尘爆炸性;随着热空气温度的提高和干燥时间的延长,煤的脱水效果变好,但当煤中水分过低时,煤样会回吸空气中的水蒸气。FTIR、SEM、TGA、XPS、BET对干燥前后煤样的表征则表明:当热空气超过170℃,干燥时间超过10min时,热空气会氧化低阶煤,导致煤中的桥键和侧链等官能团氧化;表面微观结构渐趋粉化,热应力裂纹和氧化裂隙增加;煤中孔的数量的减少,孔半径增大;煤氧复合活化能迅速降低,使煤更易与氧结合;煤表面碳元素的氧化程度逐渐加剧;这些变化都会导致煤的自燃倾向性增强。
以氮气为干燥介质的实验研究表明:在同等条件下,氮气干燥的效果明显优于空气。对干燥后煤的XPS分析也表明,氮气干燥的煤其表面被氧化的程度大为降低,干燥过程中的煤尘爆炸危险性也低,因此,采用氮气干燥具有安全、节能、环保等优点。但氮气不能低成本无限取用,开发高比例氮气循环的低温干燥工艺,才是解决低阶煤低温干燥提质的根本途径。
Low temperature convective dryness technology of high moisture contently low rank coal was investigated using hot air and nitrogen as the medium. The coal in the experiments was obtained from Shenhua Group Jinfeng Coal Colloery in Inner Mongolia. Characters of the coal are high water content, high volatile, low net calorific value and easily spontaneous combustion. The purpose of this study is to find out optimum conditions of low temperature fast dryness techonology to enhance it’s quality. At the same time, samples of the coal before and after drying were determined by FTIR, SEM, TGA, XPS, and BET to compare the effect of low temperature dryness on the functional group constitute, surface morphology, specific surface area, surface carbon valence states and oxidation kinetic parameters.
Result of the experiments indicates that the fast convective dryness process was carried out under hot air and it is flowed 2000L/min 170℃hot air is reduced the moisture from 30% to less than 15% within the 10min, the net calorific value of the coal was raised to 23.51MJ/kg, and there is no organic pollutants on dyrness exhaust gas and the process didn’t increase risk of coal dust explosion. As the hot air temperature enhanced and the drying time extended, more moisture was removed. The detection result of FTIR, SEM, TGA, XPS and BET indicated that if the hot air exceeded 170℃and drying time was more than 10min, the coal would be oxidized and a series of changes in the coal would happen, such as the bridge bond and lateral chain structure oxidation, surface micro structure was powdered and the oxidation degree of the coal surface carbon was deepened. All these changes will lead to increasing tendency of spontaneous combustion.
Experiment studies of nitrogen as the medium have shown that: the nitrogen dryness effect is better than hot air and the oxidation extents of coal surface has been reduced. However, the nitrogen couldn’t be low-cost unlimited use and development of the high proportion nitrogen cycle low temperature drying technology is the fundamental solution.
引文
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