摘要
分别以1,2,3,4-四氢萘和正二十烷模拟原料油中的芳香分和饱和分,以9-苯基蒽和9-蒽甲醛为煤中多环芳烃的模型化合物,考察了模型化合物组成、反应气氛、铁基催化剂及硫化剂形态等因素对煤-油共炼反应过程的影响,研究了煤-油共炼反应机理。结果表明:铁基催化剂不仅加快了煤的裂解,促进了氢气向活性氢的转变及向煤热解中间产物转移,同时也促进了萘加氢和四氢萘脱氢的氢传递循环供氢能力,加速了氢在整个反应网络中的二次分布;有机硫化物和单质硫在高温、高压条件下均具有良好的硫化能力。氢气转变为活性氢、进行煤液化主要通过两条途径:一是重油中芳香类化合物(如萘等)的加氢;二是氢气在催化剂表面解离吸附。煤-油共炼反应以自由基反应为主,部分碳正离子可能参与反应,形成烷基化及断键重组产物。
Coal-oil coprocessing experiments were performed with using 1,2,3,4-tetralin,n-eicosane,9-phenylanthracene and 9-anthraldehyde as model compounds.Impacts of model compound composition,reaction atmosphere,iron-based catalyst and vulcanized agent on the coal-oil coprocessing were investigated.Experimental results suggest that iron-based catalyst not only can promote coal pyrolysis,but also can help molecular hydrogen convert to active hydrogen and thus promote hydrogen donating cycle of naphthalene hydrogenation and tetralin dehydrogenation.Both organic sulfide and elemental sulfur have good sulfurization capability at high temperature and pressure.There are two main routes to transfer hydrogen into active hydrogen for coal liquefaction:hydrogenation of aromatic compounds which have hydrogen donation capability in heavy oils and dissociation of adsorbed hydrogen on the catalyst surface.It is found that free radical reaction is the main reaction during coal-oil coprocessing.Simultaneously,part of carbocations also can participate in the reaction to produce alkylation and skeleton rearrangement products.
作者
范迎利
常方园
蒋中山
石先莹
李大鹏
刘忠文
FAN Yingli;CHANG Fangyuan;JIANG Zhongshan;SHI Xianying;LI Dapeng;LIU Zhongwen(Key Laboratory of Syngas Conversion of Shaanxi Province,School of Chemistry anD_(c)hemical Engineering,Shaanxi Normal University,Xi’an 710119,China;Hydrocarbon High-Efficiency Utilization Technology Research Center,Shaanxi Yanchang Petroleum(Group)Co.Ltd.,Xi’an 710075,China)
出处
《石油学报（石油加工）》
EI
CAS
CSCD
北大核心
2021年第4期807-814,共8页
Acta Petrolei Sinica(Petroleum Processing Section)
基金
国家重点研发计划项目(2018YFB0604600-04)
中央高校基本科研业务费专项资金项目(GK201906005)基金资助
关键词
煤-油共炼
模型化合物
氢转移
反应机理
coal-oil coprocessing
model compound
hydrogen transfer
reaction mechanism
