含油污泥各组分热解相互作用的反应力场模拟研究  

Study on reaction force field simulation of pyrolysis interaction among components of oily sludge

作　　者：温燕军 蒋驰[1] 李文轩[1] 谢颖燊 王刚[1] 侯影飞[1,2] WEN Yanjun;JIANG Chi;LI Wenxuan;XIE Yingshen;WANG Gang;HOU Yingfei(State Key Laboratory of Heavy Oil Processing in China University of Petroleum,Qingdao 266580,Shandong,China;State Key Laboratory of Petroleum Pollution Control,Beijing 102206,China)

机构地区：[1]中国石油大学(华东)重质油国家重点实验室,山东青岛266580 [2]石油石化污染物控制与处理国家重点实验室,北京102206

出　　处：《化工学报》2021年第2期1100-1106,共7页CIESC Journal

基　　金：石油石化污染物控制与处理国家重点实验室开放课题(PPC2018002);国家科技重大专项项目(2016ZX05040)。

摘　　要：含油污泥中石油烃组分复杂,仅靠产物的宏观分析结果难以揭示热解过程组分之间的相互作用。以正十二烷、1-十二烯、甲基环己烷、对二甲苯和1-甲基萘五种化合物分别代表含油污泥中石油烃的链烷烃、链烯烃、环烷烃、单环芳烃和多环芳烃五种组分,构建含油污泥石油烃的模型化合物。采用基于反应力场的分子动力学模拟方法,研究了热解过程中的产物分布及各组分之间的相互作用。结果表明,模型化合物热解产物以H2和C1~3的小分子化合物为主,热解前期主要为C2H4、C3H6,热解后期主要为C2H2、C3H4和H2。相对于模型化合物中各组分单独热解,混合热解过程中石油烃各组分的消耗速率明显加快,且热解产物的片段数也有一定程度的增加。根据一级反应动力学模型,石油烃各组分在混合热解过程中的表观活化能有不同程度降低,其中链烷烃、链烯烃和环烷烃的表观活化能分别降低了16.493 kJ/mol、50.571 kJ/mol和146.289 kJ/mol,这从分子模拟层面证明了含油污泥石油烃各组分之间热解的协同作用。The composition of petroleum hydrocarbons in oily sludge is complex,and it is difficult to reveal the interaction between components in the pyrolysis process only by the macroscopic analysis results of products.Five compounds,namely n-dodecane,1-dodecene,methylcyclohexane,p-xylene,and 1-methylnaphthalene,were represented as alkanes,alkenes,cyclanes,monocyclic aromatics and polycyclic aromatic hydrocarbons in oily sludge to construct model compounds of petroleum hydrocarbon in oily sludge.The molecular dynamics simulation method based on reaction field was used to study the distribution of products and the interactions among components during pyrolysis.The results showed that the pyrolysis products of model compounds were dominated by small molecular compounds H2 and C1—3,C2H4 and C3H6 in the early pyrolysis phase,and C2H2,C3H4 and H2 in the late pyrolysis phase.Compared with the separate pyrolysis of each component in the model compound,the consumption rate of each component in the mixed pyrolysis process of petroleum hydrocarbon is obviously accelerated,and the number of pyrolysis product fragments also increases to a certain extent.According to the firstorder reaction kinetic model,the apparent activation energy of petroleum hydrocarbon components in the mixed pyrolysis process decreased to different degrees,among which the apparent activation energy of alkanes,alkenes,and cycloalkanes decreased by 16.493 kJ/mol,50.571 kJ/mol and 146.289 kJ/mol,respectively,which proved the synergistic effect of pyrolysis among petroleum hydrocarbon components of oily sludge from the level of molecular simulation.

关 键 词：含油污泥 热解 模拟 反应力场 动力学 

分 类 号：TE992.3[石油与天然气工程—石油机械设备]