沙重减渣不同溶剂萃取组分结构及对催化临氢转化性能的影响  

Study on the Structure of Fractional Extraction Components by Different SolventsFrom Saudi Heavy Vacuum Residue and Their Effects on Performance ofCatalytic Conversion Under Hydrogen Atmosphere

作　　者：侯焕娣 袁梦龙 蔡新恒 张文 王廷 董明 申海平 HOU Huandi;YUAN Menglong;CAI Xinheng;ZHANG Wen;WANG Ting;DONG Ming;SHEN Haiping(SINOPEC Research Institute of Petroleum Processing Co.,Ltd.,Beijing 100083,China;East China Engineering Science and Technology,Hefei 220022,China)

机构地区：[1]中石化石油化工科学研究院有限公司,北京100083 [2]东华工程科技股份有限公司,合肥230022

出　　处：《石油学报（石油加工）》2024年第5期1373-1384,共12页Acta Petrolei Sinica(Petroleum Processing Section)

基　　金：中国石化股份有限公司科研项目(121008)基金资助。

摘　　要：以甲苯、正戊烷、正庚烷、正庚烷/甲苯体积比3/1的混合溶剂4种溶剂分级萃取沙特重质减压渣油(沙重减渣)获得的可溶物及不溶物为原料,脱沥青油(DAO)、催化柴油(LCO)和催化油浆(FCC-slurry oil)为溶剂油,在反应温度415℃、氢初压7 MPa、萃取组分质量分数10%、催化剂质量分数1000μg/g以及反应时间1 h的条件下进行催化临氢热转化实验,研究分级萃取组分结构特征、临氢反应性能差异以及溶剂油对戊烷沥青质转化的影响。研究结果表明,沙重减渣5种分级萃取组分分子以孤岛型结构为主,含硫化合物所占比例超过70%,每个分子至少含有1~2个硫原子。催化临氢反应结果表明,分级萃取组分中富含的多硫化合物通过定向加氢-选择性脱硫反应路径,同时实现脱硫及孤岛型结构轻质化,使得5种分级萃取组分(戊烷沥青质(C5As)、庚烷可溶物(C7S)、庚烷沥青质(C7As)、混合溶剂1可溶物(M1S)、混合溶剂1沥青质(M1As))的总转化率均大于97%,其中C7S、C5As及M1S 3种组分的轻质化率大于94%;当从C5As中萃取分离出C7S后得到C7As, C7As临氢转化缩合率增加了218%,通过研究发现,C7S对C7As良好的溶解及较高的饱和溶解度是移除C7S后C7As临氢反应缩合率显著增加的本质原因。3种溶剂油抑制戊烷沥青质临氢反应缩合反应的能力由大到小顺序为LCO>FCC-slurry oil>DAO,这与溶剂油LCO的饱和组分含量较低以及在反应过程承担传氢作用的纯芳烃含量最高(质量分数大于91.5%)密切相关。Using the soluble and insoluble substances obtained from the fractional extraction of Saudi heavy vacuum residue by four different solvents including methylbenzene,n-pentane,n-heptane,and the mixture of n-heptane and methylbenzene at a volume ratio of 3/1 as raw materials and the deasphalted oil(DAO),catalytic diesel oil(LCO)and FCC-slurry oil as solvent oils,the catalytic hydrogenation thermal conversion were conducted at the temperature of 415℃,hydrogen initial pressure of 7 MPa,extraction component mass fraction of 10%,and catalyst mass fraction of 1000μg/g and reaction time for 1 h.This aims to study the structural characteristics of extraction components,the difference in performance of thermal reaction under hydrogen atmosphere,and the influence of solvent oils on the conversion of pentane asphaltene.The results indicate that the molecular structure of the five extraction components from Saudi heavy vacuum residue is mainly of the isolated island type,with the composition of sulfur compounds accounting for over 70%,and each molecule contains at least 1—2 sulfur atoms.The catalytic thermal reaction under hydrogen atmosphere shows that polysulfide compounds can achieve not only desulfurization but also lightweighting of the components with isolated island type structure through the directed hydrogenation-selective desulfurization reaction path,which can be also converted into aromatic compounds.This is a key reaction for the total conversion rate of five fractionated extraction components,i.e.,n-pentane asphaltene(C5As),n-heptane soluble substance(C7S),n-heptane asphaltene(C7As),mixed solvent 1 soluble substance(M1S),and mixed solvent 1 asphaltene(M1As),to exceed 97%,and the lightweighting rates of C7S,C5As,and M1S are greater than 94%.C7As was obtained after the extraction separation of C7S from C5As,and the condensation rate of C7As was increased by 218%in catalytic conversion under hydrogen atmosphere.Through further research,it has been found that the good solubility and high saturation solubility of

关 键 词：分级萃取 催化临氢反应 溶解度参数 含硫化合物 孤岛型结构转化 溶剂油传氢 

分 类 号：TE624[石油与天然气工程—油气加工工程]