煤直接液化条件下萘-四氢萘加氢转化反应行为

Hydroconversion Behavior of Naphthalene-tetrahydronaphthalene Under Direct Coal Liquefaction

以纳米Fe2O3为催化剂,在0.5 L高压釜中考察了反应压力19 MPa下,不同反应温度(435℃~465℃)和反应时间(0 min^120 min)对萘-四氢萘体系加氢转化过程及产物分布的影响。根据实验结果和分析,建立了萘-四氢萘体系加氢转化反应机理模型,通过优化算法求解得到各反应的反应速率常数和活化能。结果表明:萘很快达到转化平衡状态,且低温和长停留时间有利于萘的加氢转化;萘的加氢反应速率高于四氢萘的脱氢反应速率,在四氢萘的加氢反应中,以异构化反应为主,主要生成甲基茚满和丁基苯。反应物萘、四氢萘、十氢萘(反)、十氢萘(顺)、1-甲基茚满、正丁基苯和烷基苯的质量分数的实验值和模拟值的相对偏差分别为4.56%,1.35%,9.60%,7.24%,8.29%,10.64%和10.07%。

The hydrogenation conversion behavior of naphthalene-tetrahydronaphthalene system was investigated in a 0.5 L autoclave with nano Fe2O3 as catalyst.When the reaction pressure was 19 MPa,different reaction conditions including temperatures(435℃-465℃)and reaction time(0 min-120 min)were applied to investigate their effects on the hydrogenation conversion process and product distribution of naphthalene-tetrahydronaphthalene reaction.According to the experimental results,the mechanism model of hydrogenation reaction of naphthalene-tetrahydronaphthalene system was established.The reaction rate constant and activation energy of each reaction were obtained by using the optimization algorithm.The results show that naphthalene quickly reaches the equilibrium state of conversion,and low temperature and long residence time are beneficial to the hydroconversion of naphthalene.In addition,the hydrogenation reaction rate of naphthalene is higher than the dehydrogenation reaction rate of tetrahydronaphthalene,and during the hydrogenation reaction of tetrahydronaphthalene,the isomerization reaction is dominant with the primary products of producing methylindane and butylbenzene.The relative deviations between the experimental and simulated values of mass fraction of the products naphthalene,tetrahydronaphthalene,trans-decahydronaphthalene,cis-decahydronaphthalene,1-methyl indane,n-butylbenzene and alkylbenzene were 4.56%,1.35%,9.60%,7.24%,8.29%,10.64%and 10.07%respectively.