Mo-Ni催化下褐煤热溶物的生成机理  

Formation mechanism of soluble portion of indonesian lignite by catalysis of Mo-Ni

作　　者：赵欢[1,2] 王鑫 焦忠泽[1] 曾文 窦金孝[3] 刘宇[1] 余江龙[2,3] ZHAO Huan;WANG Xin;JIAO Zhong-ze;ZENG Wen;DOU Jin-xiao;LIU Yu;YU Jiang-long(Institute of Thermal Energy,Shenyang Aerospace University,Shenyang 110136,China;Chemical Engineering,University of Newcastle,Callaghan,NSW 2308,Australia;Key Laboratory of Advanced Coal and Coking Technology of Liaoning Province,University of Science and Technology Liaoning,Anshan 114051,China)

机构地区：[1]沈阳航空航天大学,热能研究所,沈阳110136 [2]Chemical Engineering,University of Newcastle,Callaghan,NSW 2308,Australia [3]辽宁科技大学清洁能源与燃料化学研究所,辽宁鞍山114051

出　　处：《沈阳航空航天大学学报》2020年第3期33-40,共8页Journal of Shenyang Aerospace University

基　　金：国家自然科学基金(项目编号:51675351);国家公派留学基金(项目编号:201608210120);沈阳市科技局计划项目(项目编号:RC170194)。

摘　　要：利用Mo-Ni催化剂在不同热溶温度下对印尼褐煤进行热溶解聚,对比分析Mo-Ni对热溶物组分生成和成分分布的影响规律,研究Mo-Ni催化下褐煤热溶物的生成机理。GCM S分析结果表明:起初物理热溶生成少量带有长直链的酯,随着热溶温度的升高,酯类增加的同时更多分子量较小的酯生成,继续升高温度,酯类的相对含量急剧减少,芳烃和酚成为主要组分。Mo-Ni作用下,β断裂和脱氢反应使得长直链的烷酸甲酯生成短链烷酸甲酯、正构烷烃和单不饱和烯烃;其中短链烷酸甲酯发生催化裂化、脱羧、脱羟、加氢和脱氧等一系列反应直接或间接生成正构烷烃。Mo-Ni的低聚活性和酸性进一步将正构烷烃和单不饱和烯烃转变为低碳烯烃,而烯烃聚合生成苯环;苯环发生甲基化、亲核取代,聚合等反应生成芳烃和酚。Thermal dissolutions( TD) of Indonesian lignite at different temperatures and by catalysis of M o-Ni or not were carried out to analyze the effects of M o-Ni on the constituent ingredient and composition distribution of soluble portion. Formation mechanism of the soluble portion was also investigated.The results of GC-M S analysis show that a small amount of esters with long straight chains initially formed caused by physical thermal dissolutions. With the increase of temperature,the esters increase,but more esters are comprised of smaller molecular. The further increase of the temperature,relative content of the esters drastically reduce,aromatic hydrocarbons and phenols become the main constituent ingredient of the soluble portion. Under the action of M o-Ni,beta scission and dehydrogenation lead to the formation of short-chain methyl alkanoate,n-alkanes and 1-alkenes from long-chain methyl alkanoate. The short-chain methyl alkanoate further produce n-alkanes directly or indirectly by a series of reactions,such as catalytic cracking,decarboxylation,dehydroxylation,hydrogenation and deoxidation. The n-alkanes and 1-alkenes transform into low-carbon olefins caused by oligomeric activity and acidity of M oNi,and then the olefins are polymerized to benzene rings. The rings are methylated,nucleophilic substituted,and polymerized to produce aromatic hydrocarbons and phenols.

关 键 词：褐煤 热溶解聚 Mo-Ni催化剂 烷酸甲酯 生成机理 

分 类 号：TQ533[化学工程—煤化学工程]