煤液化残渣结构演变及其高软化点包覆沥青制备表征  

Structural evolution of coal liquefaction residue and preparationcharacterization of coated pitch with high softening point

作　　者：要辉 吴永杰[1] 阮如玉 魏建明 刘均庆 Yao Hui;Wu Yong-Jie;Ruan Ru-yu;Wei Jian-ming;Liu Jun-qing(China Shenhua Coal to Liquid Chemical Co.,Ltd.,Ordos Coal to Liquid Branch,Ordos,Inner Mongolia Erdos 017209,China;Beijing Low Carbon Clean Energy Research Institute,Beijing 102211,China)

机构地区：[1]中国神华煤制油化工有限公司鄂尔多斯煤制油分公司,内蒙古鄂尔多斯017209 [2]北京低碳清洁能源研究院,北京102211

出　　处：《炭素技术》2024年第4期60-69,共10页Carbon Techniques

摘　　要：通过煤制油35万t油渣萃取装置对煤液化残渣进行脱灰脱固,获得了低灰煤液化精制沥青,并采用不同溶剂将其分离得到重油、沥青烯和前沥青烯3个组分,初步构建了平均分子结构模型。结果表明:3个组分的基本结构都是环烷烃、稠环芳烃链接烷基侧链、并含有杂原子的单元组成,结构单元之间形成地合体。各分子活性中心主要分布在苯环的双键以及活性原子O区域,沥青烯和前沥青烯具有较高的活性。为充分利用煤液化精制沥青,通过空气氧化法制备高软化点包覆沥青,探索空气流量、氧化温度及时间对制备出的包覆沥青软化点和结焦值的影响,并利用ATR傅里叶变换红外光谱、X射线光电子能谱、NMR核磁共振波谱对氧化缩聚过程展开分析总结。结果表明,当搅拌转速360 r/min,反应时间2~3 h,反应温度310~320℃,空气流量1.5~2 L/min时,可以制得软化点205℃和软化点245℃的高品质包覆沥青。随后,开展了原始石墨、石油系包覆沥青与上述2种批次的煤液化包覆沥青的电化学性能平行对比试验,结果表明:245℃的煤液化包覆沥青在倍率、长循环性能比280℃油系包覆沥青有较大性能优势,可有效改善原始石墨电化学性能,此研究拓宽了煤液化沥青的应用领域,提供了一种制备包覆沥青的新思路。The low ash coal liquefaction refined pitch was obtained by deashing and desolidifying through the 350,000 t oil residue ex⁃traction device of coal-to-oil Company,and was separated by different solvents to get heavy oil,asphaltene and pre-asphaltene.An av⁃erage molecular structure model was initially constructed,And the results show that the basic structures of the three components are cy⁃cloalkanes,polycyclic aromatic hydrocarbon linked alkyl side chains and units containing heteroatoms.And the structural units form a complex between them.The active centers of each molecule are mainly distributed in the double bonds of the benzene ring and the O re⁃gion of the active atom,and asphaltene and pre-asphaltene have high activity.In order to fully utilize coal liquefaction refined pitch,a high softening point coated pitch was prepared by air oxidation method.The effects of air flow rate,oxidation temperature and time on the softening point and coking value of the prepared coated pitch were explored.The oxidation condensation process was analyzed and summarized using ATR Fourier transform infrared spectroscopy,X-ray photoelectron spectroscopy,and NMR nuclear magnetic reso⁃nance spectroscopy.The results show that when the stirring speed is 360 r/min,the reaction time is 2~3 h,the reaction temperature is 310~320℃,and the air flow rate is 1.5~2 L/min,high-quality coated pitch with a softening point of 205℃and 245℃can be pro⁃duced,respectively.Subsequently,the parallel comparative tests for the electrochemical properties were conducted on the original graph⁃ite,petroleum based coated pitch,and the two batches of coal liquefaction coated pitch mentioned above.The results show that coal liq⁃uefaction coated pitch with a softening point of 245℃has significant performance advantages in terms of rate and long cycle perform⁃ance compared to oil based coated pitch with a softening point of 280℃,which can effectively improve the electrochemical performance of raw graphite,broaden the application field o

关 键 词：煤液化沥青 沥青烯 前沥青烯 氧化聚合 包覆沥青 

分 类 号：TQ522.65[化学工程—煤化学工程]