煤/重油加氢共炼中沥青质的转化规律  

Conversion of Asphaltenes in Hydro-coprocessing of Coal and Heavy Oil

作　　者：邓文安[1] 刘聪聪 杨腾飞 秦勇[1] 李传[1] 尹崇杰 DENG Wenan;LIU Congcong;YANG Tengfei;QIN Yong;LI Chuan;YIN Chongjie(State Key Laboratory of Heavy Oil Processing,China University of Petroleum,266580 Qingdao,China)

机构地区：[1]中国石油大学(华东)重质油国家重点实验室

出　　处：《煤炭转化》2019年第5期37-46,共10页Coal Conversion

基　　金：国家自然科学基金青年基金项目(21106186);山东省自然科学基金面上项目(ZR2017MB026)

摘　　要：以安徽褐煤为原料煤、钼酸铵为催化剂,分别采用马瑞常渣(MRAR)和克拉玛依常渣(KAR)为原料油在高压釜内模拟煤/重油加氢共炼反应。在MRAR体系和KAR体系达到反应温度400℃后反应0 min和60 min时,提取产物中的沥青质和固体残渣,采用元素分析、FTIR、XRD、^13C NMR和SEM等手段分析其结构及微观形貌变化。结果表明:反应0 min和60 min时,与MRAR体系相比,KAR体系中沥青质的脂肪侧链都较长,且芳香片层的直径和高度较大,更易于缩合生焦,因此其干基无灰煤转化率低于MRAR体系干基无灰煤转化率。反应0 min时,KAR体系中沥青质的特征更接近煤液化沥青质的特征,此后随着次生沥青质的增多,KAR体系中沥青质的芳香片层高度与MRAR体系中沥青质的芳香片层高度差异明显减少。反应60 min时,共炼体系中固体残渣的脂肪链结构与其沥青质的脂肪链结构相似,表明部分固体残渣是沥青质缩合生焦形成的。SEM对比分析则进一步说明了共炼体系中沥青质是复杂的混合产物,随反应进行KAR体系相比MRAR体系形成了更多焦炭。A kind of Anhui lignite was used as raw coal,and Merey atomospheric residue(MRAR)and Karamay atomospheric residue(KAR)were respectively selected with ammonium molybdate as catalyst,for the simulation of hydro-coprocessing of coal and heavy oil.MRAR and KAR system were respectively conducted at reaction temperature of 400℃for 0 min and 60 min,to collect the asphaltenes and solid residues in products.The structure changes and microscopic morphology variations of the asphaltenes and solid residues were analyzed by ultimate analysis,FTIR,XRD,13 C NMR and SEM.Experimental results show that longer aliphatic side chains and larger diameter of aromatic sheet with higher stack height are observed for the asphaltenes in KAR system at different reaction time,and more coke is formed in KAR system than that in MRAR system.Thus,the coal conversion is lower in KAR system than that in MRAR system.The features of asphaltenes in KAR system at the beginning stage is closer to the features of coal liquefaction asphaltenes,whereas the stack height difference of aromatic sheets between asphaltenes in KAR system and in MRAR system significantly decreases,since the increase of secondary asphaltenes in reaction system.However,at the late stage in the reaction,there exists certain similarity in side chain structure between solid residues and asphaltenes from coprocessing system,which indicates that partial solid residues are derived from the condensation of asphaltenes.Contrast of SEM photos further display that obtained asphaltenes from coprocessing system belong to complex mixtures,and more coke is formed in KAR system than that in MRAR system with the reaction.

关 键 词：煤/重油加氢共炼 干基无灰煤转化率 沥青质 固体残渣 生焦 

分 类 号：TQ529.1[化学工程—煤化学工程]