2种高温沥青结构表征及热解特性  

Structural and pyrolysis characteristics of two high-temperature pitches

作　　者：周星苗 杨桃[1] 宋燕[1,2] 刘占军 ZHOU Xingmiao;YANG Tao;SONG Yan;LIU Zhanjun(Key Laboratory of Carbon Materials,Institute of Coal Chemistry,Chinese Academy of Science,Taiyuan 030001,China;Center of Materials Science and Optoelectronics Engineering,University of Chinese Academy of Science,Beijing 100049,China)

机构地区：[1]中国科学院山西煤炭化学研究所中国科学院炭材料重点实验室,山西太原030001 [2]中国科学院大学材料与光电研究中心,北京100049

出　　处：《洁净煤技术》2023年第2期80-91,共12页Clean Coal Technology

基　　金：国家自然科学基金资助项目(52072383,U21A2061);中科院山西煤化所创新基金资助项目(SCJC-XCL-2022-08)。

摘　　要：采用族组分分析、元素分析、红外光谱(FT-IR)、核磁共振(NMR)、凝胶渗透色谱(GPC)等分析表征手段对神华煤液化沥青(CLP,软化点为403.15 K)和永东煤焦油沥青(CTP,软化点为383.65 K)进行了结构解析,结合计算的平均分子结构参数得到2种沥青可溶组分的平均分子结构模型;通过热重(TG)分析2种沥青的热解特性,并利用Coats-Redfern和DAEM两种动力学模型对其进行热解动力学计算。结果表明:与CTP相比,CLP的芳香性较差、缩合程度较低。2种沥青的热解过程分为3个阶段,主要热解阶段在473.15~873.15 K。其中CLP因其分子量分布较窄且分子结构缩合程度较小有较集中剧烈的热解过程;CLP的热解产物释放特性指数RH较大。由Coats-Redfern法计算的煤液化沥青和煤焦油沥青的平均活化能分别为35.03和37.98 kJ/mol;DAEM模型中,随转化率α增大,2种沥青的活化能呈增长趋势,α>0.5,活化能增加明显;从C-R模型和DAEM模型的拟合系数R2可知,2种模型对煤焦油沥青的热解过程适用性更好。Shenhua coal liquefaction pitch(CLP,softening point:403.15 K)and Yongdong coal tar pitch(CTP,softening point:383.65 K)were analyzed using group composition analysis,elemental analysis,FT-IR,NMR and GPC.The average molecular structure model of the soluble were obtained.The pyrolysis characteristics of CLP and CTP were analyzed by TG,and the kinetics were calculated by Coats-Red⁃fern and DAEM models,respectively.The results show that the CLP has lower aromatization and condensation degree compared with the CTP.The pyrolysis of the two pitches can be divided into three stages with the main process ranges from 473.15-873.15 K.CLP has con⁃centrated pyrolysis process due to the narrow molecular weight distribution and small degree of condensation of molecular structure.The py⁃rolysis product release index RH of CLP is larger.The average activation energy calculated by the Coats-Redfern method is 35.03 kJ/mol for CLP and 37.98 kJ/mol for CTP.In the DAEM model,with the increase of conversionα,the E of the two pitches increase.The E in⁃creases significantly especially whenα>0.5.According to the fitting correlation coefficient R2 of the two kinetic models,the C-R model and DAEM model are suitable for the pyrolysis process of CTP.

关 键 词：煤液化沥青 煤焦油沥青 结构解析 热解特性 热解动力学 

分 类 号：TQ536[化学工程—煤化学工程]