【作者】 郭庆洲；

【导师】 李大东；

【作者基本信息】 石油化工科学研究院 ， 有机化工， 2000， 博士

【摘要】 在“九五”期间，石油化工研究院(RIPP)开发了在中压条件下以中间基原油生产高粘度指数润滑油基础油的成套技术。为了使该技术能成功地推广应用，对该过程的反应动力学行为、进料及反应条件对基础油组成、粘度指数、光安定性的影响进行了研究。 在300mL中型加氢处理装置上，以伊朗轻原油的减三线馏分油及其浅度糠醛精制油和常规糠醛精制油为原料，反应条件为温度360～380℃，氢分压6.4～12.0MPa，氢油比(体积比)1000：1，空速0.3～1.5h-1范围内，对润滑油加氢处理过程的三集总反应动力学模型、五集总反应动力学模型，加氢处理进料和反应条件对基础油组成、粘度指数及光安定性的影响进行了系统研究。 加氢处理集总反应动力学模型的研究结果表明：在润滑油中压加氢处理过程中，发现以二级反应描述反应体系中芳烃的转化，以一级反应描述其它组分的转化建立三集总和五集总反应动力学模型，能很好地与实验数据拟合。动力学参数的计算结果表明，在一定温度下，进料不同时，各个集总组分的反应速率常数不同，随进料精制深度的增大，各个集总组分的反应速率常数均有不同程度的增加；发现各集总组分的反应速率常数与进料芳烃含量Y。的简单函数C+=1nY。呈线性关系，C+可以定义为衡量润滑油加氢处理进料质量指标的参数。在一定的进料和实验压力下，温度对反应速率常数的影响表现为：随温度的提高，芳烃的反应速率常数变化不大，其它组分的反应速率常数变化较大；对一定的进料 石油化工科学研究院博士学位论文在给定的温度下，氢分压对各个集总组分的反应速率常数的影响为：提高氢分压时，芳烃的反应速率常数增大，并发现氢分压对芳烃反应速率的影响程度与（也呈线性关系。而其它集总组分的反应速率常数随氢分压的提高无明显变化。 进料和反应条件对基础油组成和粘度指数有重要影响，研究结果表明：当进料的芳烃含量较低时，基础油中饱和烃的含量较高，其中的芳香烃和环烷烃主要以环数较少的烃类形式存在；当进料中芳烃含量较高时，基础油中的饱和烃含量降低，芳烃的含量增加，基础油中不同环数的环烷烃和芳香烃的含量趋向于按照环数呈均匀分布趋势；在中压反应条件下，反应温度对基础油中芳烃含量的变化影响较小，但对其它组分的影响较大，特别是三环以上的环烷烃，随反应温度提高，它们在基础油中的含量明显减少；提高氢分压可以明显降低基础油中的芳烃含量。 加氢处理基础油的粘度指数与其组成有密切关系，随看基础油中芳香烃含量的降低和链烷烃含量的提高，粘度指数增大；发现环烷烃与粘度指数之间的关系不是单调的，在粘度指数从小到大的变化过程中，环烷烃在基础油中的含量出现峰值；在此基础油上，本文提出采用分段方法对基础油粘度指数和组成进行关联的思想，所建立的粘度指数与基础油组成之间的关联模型对粘度指数的预测具有较高的精度。 对加氢处理基础油光安定性的研究结果表明：影响加氢处理基础油光安定性的主要因素是加氢处理过程未能完全转化的多环芳烃，当加氢处理基础油含有较少的多环芳烃时具有较好的光安定性。 11 中压加氢处理从中间基原油制取高粘度指数润滑油基础油研究 本文首次对润滑油中压加氢处理过程的动力学行为、进料组成及反应条件对基础油组成和粘度指数的影响进行了系统地研究，所．得到的动力学模型，进料及反应条件对基础油性质的影响规律可以应用于预测加氢处理基础油的收率、组成和粘度指数；也可用于对润滑油中压加氢处理过程进行仿真和优化，以确定进料的溶剂精制深度或选择加氢处理的最佳反应条件，对于指导科研和实际生产具有重大的现实意义。更多还原

【Abstract】 A medium pressure hydrotreating process for manufacturing high-grade lube oil base stocks has been developed by RIPP. In order to have this technology used successfully in refinery, the reaction kinetics, influence of hydrocarbon composition of feedstocks and reaction conditions on lube base oil stocks are studied.All hydrotreating tests are conducted in a 300mL pilot plant. The test conditions are temperature of 360- 380 0C, hydrogen partial pressure of 6.4-12.OMPa, 112/Oil ratio of 1000 Nm3/m3 and LHSV of 0.3-l.5h’. Feedstocks used in tests are Iranian light crude VGO, its raffinate by mild furfural solvent refining and raffinate by conventional furfural solvent refining. With those feedstocks, a three-lumping kinetic model and a five-lumping kinetic model are developed, the influence of feedstocks and test conditions on the composition, VI (Viscosity Index) and photostability of lube oil base stocks produced is also investigated intensively.It is found that those two kinetic models can fit the experimental data satisfactorily with second reaction order to aromatics and first reaction order to other components. The result of parameters’ calculation indicates that the property of feedstocks affects rate constants greatly, lumping components of the feed with less aromatics have larger rate constants than that of feed with more aromatics. At the test condition of hydrogen partial pressure eiiiployed, temperature has little affect on rate constant of aromatic component, but great function to that of others. On contrast, pressure has great affect on rate constant of aromatics. As hydrogen partial pressure increasing, the rate constant of aromatics becomes large, but the rate constants of other components have little changed.The distribution pattern of composition of hydrotreated base oils is different according to various feedstocks and test conditions. The feedstock containing less aromatics content makes hydrotreated base oils mainly be composed of isoparaffin and mononuclear or dinuclear naphthenic hydrocarbon and mononuclear aromatics. At the test condition of hydrogen partial pressure employed, temperature has little affect to aromatics, but the amount of tn-nuclear and tetra-nuclear naphthenic hydrocarbon in base oils is decreased evidently as temperature is increased. Hydrogen partial pressure is only to promote the disappearance of aromatics tremendously.VI has close correlation to the group chemical composition of hydrotreated lube oil base stocks. With the increasing content of isoparaffln and the decreasing content of aromatics, VI is increased. Naphthenic hydrocarbon is not a monotonic function of VI, it emerges a peak value as VI changes.The photostability of hydrotreated lube oil base stocks becomes worse when there is a large amount of polyaromatics in it. The polyaromatics, which have not been completely hydrogenated in hydrotreating process, is the key factor to ruin the oil photo-property. The result of photo-test indicates that the stability of base oils is good when there is little polyaromatics in it.更多还原