原油直接加氢改质及其沥青质超分子解缔反应的研究  

Research on direct hydro-upgrading of crude oils and the dissociation of asphaltene supramolecules

作　　者：许顺年 冯晓 史得军 孙志国 张宸玮 王刚[1] 高金森[1] 徐春明[1] XU Shunnian;FENG Xiao;SHI Dejun;SUN Zhiguo;ZHANG Chenwei;WANG Gang;GAO Jinsen;XU Chunming(State Key Laboratory of Heavy Oil Processing,China University of Petroleum,Beijing 102249,China;Petrochemical Research Institute of PetroChina,Beijing 102206,China)

机构地区：[1]中国石油大学(北京)重质油全国重点实验室,北京102249 [2]中国石油石油化工研究院,北京102206

出　　处：《化工学报》2025年第2期812-824,共13页CIESC Journal

基　　金：国家自然科学基金面上项目(42020619);中国石油天然气基团有限公司基金项目(2023ZZ36,2022DJ6003)。

摘　　要：加氢处理是劣质重油提质升级的重要工艺,但是沥青质超分子的存在严重影响了加氢改质的效果。因此,针对沥青质超分子三个主要层级结构(分子单元、纳米聚集体和团簇),提高其加氢解缔效率至关重要。本研究考察了原油直接加氢的反应性能及沥青质超分子层级结构的变化规律,旨在为提高石油中沥青质超分子解缔效率提供新的解决方案。结果表明,与重油加氢相比,原油直接加氢表现出更优异的改质性能,其中非烃化合物的脱除率超过70%,而沥青质的脱除率则超过80%。在原油加氢过程中,沥青质的表观结构尺寸从原先的2~4μm降低到2μm以下,且颗粒尺寸变得更加均匀。沥青质超分子的层级结构也发生了显著变化,超分子团簇的尺寸相比加氢前减少了50%以上,沥青质超分子中90%的非晶纳米聚集体被转化,而难以转化的似晶纳米聚集体的转化率也超过了70%。原油加氢处理降低了分子单元之间的空间屏蔽效应,使其形成了更紧密的次级结构。本研究探索了原油直接加氢改质的新方法,以提高沥青质超分子解缔性能,促进劣质原油的高效利用。Hydrotreating is a crucial process for upgrading low-quality heavy oils.However,the presence of asphaltene supramolecules severely impedes the efficiency of hydrogenation.Therefore,it is very important to improve the hydrogenation decomposition efficiency of asphaltene supramolecular in three main hierarchical structures(molecular unit,nanoaggregate and cluster).This study investigated the reaction performance of direct hydrogenation of crude oil and the change law of asphaltene supramolecular hierarchical structure,aiming to provide a new solution for improving the asphaltene supramolecular decomposition efficiency in petroleum.The results indicate that direct crude oil hydrogenation performs better in upgrading than heavy oil hydrogenation,achieving a removal rate of over 70%for non-hydrocarbon components and more than 80%for asphaltenes.During the crude oil hydrogenation,the apparent structural size of asphaltene decreased from a range of 2—4μm to below 2μm,resulting in a more uniform particle size.The hierarchical structure of asphaltene supramolecules has changed significantly.The size of supramolecular clusters has decreased by over 50%compared to their size before hydrogenation.Additionally,nearly 90%of the amorphous nanoaggregates in asphaltene supramolecular structures have been converted,and the conversion of difficult-to-convert crystalline nanoaggregates has exceeded 70%.Hydrogenating crude oils decrease the spatial shielding effect among molecular units,resulting in a more compact secondary structure.This study investigated a novel method for the direct hydrogenation of crude oils,aiming to enhance the dissociation of asphaltene supramolecules and facilitate the efficient conversion of low-quality crude oils.

关 键 词：原油 加氢 沥青质 聚合 解缔 层级结构 

分 类 号：TE624[石油与天然气工程—油气加工工程]