Fissure evolution and variation of pyrolysis kinetics parameters of tar-rich coal during heat treatment under different atmosphere
WANG Shuangming;SUN Qiang;HU Xin;GE Zhenlong;GENG Jishi;XUE Shengze;SHI Qingmin
陕西省煤炭绿色开发地质保障重点实验室西安科技大学 煤炭绿色开采地质研究院西安科技大学 地质与环境学院山西大同大学 建筑与测绘工程学院
富油煤的清洁高效开发有助于保障我国的能源安全。选择柠条塔矿富油煤,开展了N2和欠氧气氛条件下的加热试验,利用体视显微镜获取不同温度处理后富油煤的表观形貌,在氩气气氛中,对富油煤在0~600 ℃下热重(TG)、微商热重(DTG)、差示扫描量热(DSC)进行测试,基于激光闪射法监测富油煤热导率变化,并分析了不同升温速率下活化能、频率因子等热解动力学参数的变化规律,探讨富油煤热处理后裂隙演化和热解动力学参数变化。研究结果表明:随着加热温度的升高,富油煤表面裂隙数目明显增多,逐渐贯通,且镜煤裂隙发育程度更高。相比N2气氛,同温度下欠氧气氛中煤样裂隙率更高。质量损失率变化趋势与裂隙率相似,由于欠氧环境中煤样发生氧化反应,导致其增速更快。N2气氛中富油煤质量损失率与裂隙率迅速提升的温度点明显滞后于欠氧气氛。室温至350 ℃范围内,由于热膨胀影响,富油煤热导率随着温度升高有所增加。根据热重分析,富油煤随温度变化可分为室温至300 ℃、300~500 ℃和500~600 ℃ 3个阶段,在阶段Ⅰ和Ⅱ分别由于吸附水析出和有机质的分解吸热,频率因子和活化能逐渐增大;在阶段Ⅲ由于无机矿物的分解放热,频率因子和活化能降低。研究结果有助于理解富油煤高温开发过程中的结构演化机制和传热机理。
The clean and efficient development of tar-rich coal is helpful in ensuring China's energy security. The tar-rich coal from Ningtiaota Mine was selected and heated under N2 and hypoxia atmosphere. Using a stereomicroscope to obtain the apparent morphology of tar-rich coal treated at different temperatures, the thermal gravimetric (TG), differential scanning calorimetry (DSC), and differential scanning calorimetry (DTG) of tar-rich coal were tested at 0-600 ℃ in an argon atmosphere. Based on the laser flash method, the thermal conductivity changes of tar-rich coal were monitored, and the changes in pyrolysis kinetics parameters such as activation energy and frequency factor under different heating rates were analyzed. The crack evolution and pyrolysis kinetics parameter variation of tar-rich coal after heat treatment were explored. The results show that with the increase of heating temperature, the number of cracks on the surface of the tar-rich coal sample increases significantly and gradually. Additionally, the degree of fracture development in vitrain is higher. Compared with the N2 atmosphere, the crack rate of coal samples in the hypoxia atmosphere at the same temperature is higher. The changing trend of mass loss ratio is similar to the trend of fracture rate, and the growth rate is faster due to the oxidation reaction of coal samples in the hypoxia environment. The temperature at which the mass loss rate and fracture rate of tar-rich coal rapidly increase in the N2 atmosphere is clearly lagging behind that in the hypoxia atmosphere. In the range of room temperature to 350 ℃, due to the effect of thermal expansion, the thermal conductivity of tar-rich coal increases with the increase of temperature. According to TG analysis, the tar-rich coal can be divided into three stages with temperature changes: 25-300 ℃, 300-500 ℃ and 500-600 ℃. In stages I and II, due to the precipitation of adsorbed water and the heat absorption of organic matter decomposition, the frequency factor and activation energy gradually increase; In stage III, due to the exothermic decomposition of inorganic minerals, the frequency factor and activation energy decrease. The results are help understand the structural evolution mechanism and heat transfer mechanism of tar-rich coal in the process of high temperature development.
tar-rich coal;high temperature;cracks;thermal analysis;pyrolysis kinetics
主办单位:煤炭科学研究总院有限公司 中国煤炭学会学术期刊工作委员会