渣油加氢过程中硫化物的转化规律研究  

Research on the Transformation Law of Sulfur Compounds During Residue Hydrotreating Process

作　　者：施瑢 邓中活 刘涛 任亮 戴立顺 SHI Rong;DENG Zhonghuo;LIU Tao;REN Liang;DAI Lishun(SINOPEC Research Institute of Petroleum Processing Co.,Ltd.,Beijing 100083,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

出　　处：《石油学报(石油加工)》2025年第2期416-424,共9页Acta Petrolei Sinica(Petroleum Processing Section)

基　　金：中国石油化工股份有限公司项目(2021YFA1501204)基金资助。

摘　　要：采用傅里叶离子回旋质谱对渣油原料及其脱硫率为55.9%~97.6%的7种加氢生成油进行分析,获得了渣油加氢过程中硫化物的转化规律及难脱除硫化物的分子结构特征。分析结果显示,加氢生成油中剩余的S 1类化合物(含有1个硫原子的化合物)为难脱除的硫化物,S 2类化合物(含有2个硫原子的化合物)和S 3类化合物(含有3个硫原子的化合物)反应活性更高的原因在于其具有更高的竞争吸附优势和更低的空间位阻;在渣油深度加氢脱硫过程中,S 1类化合物依次被完全脱除最可能的顺序由大到小为:噻吩类(T)>苯并噻吩类(BT)>五环以上噻吩类(5R-p)>五环噻吩类(5R)>苯并萘并噻吩类(BNT)>二苯并噻吩类(DBT),这是由于T和BT类硫化物的空间位阻最小,而DBT、BNT、5R和5R-p类硫化物的加氢脱硫反应活性顺序与其芳烃饱和反应活性顺序一致;最难脱除硫化物的等效双键数和碳数分别为9~12和36~39,即最难脱除的硫化物主要为侧链取代碳数为20~27的BNT和DBT类硫化物,这类硫化物的脱除需要通过先加氢后脱除的路径进行。The residual oil and seven of its hydrogenated oils with a hydrodesulfurization rate ranging from 55.9%to 97.6%were analyzed by Fourier ion cyclotron mass spectrometry to obtain the transformation law of sulfur compounds and the molecular structure characteristics of the most refractory sulfur compounds in the residue hydrotreating process.The analysis results show that the residual S 1 type compounds with 1 sulfur atom in the hydrogenated oil are the refractory sulfur compounds.For S 2 and S 3 type compounds with 2 and 3 sulfur atoms,respectively,the reactivity is higher due to their higher competitive adsorption advantages and lower steric hindrance.In the deep hydrodesulfurization process for residue oil,the S 1 type compounds that can be possibly completely removed are list below in a descending order:thiophenes(T)>benzothiophenes(BT)>thiophenes with more than 5 rings(5R-p)>thiophenes with 5 rings(5R)>benzonaphthalene thiophenes(BNT)and dibenzothiophenes(DBT).This is because T and BT compounds have the least steric hindrance.In contrast,the reactivity sequence of DBT,BNT,5R,and 5R-p compounds is consistent with that of their aromatic saturation reaction.The most refractory sulfur compounds have Dowble bond equivalents ranging from 9 to 12 and carbon numbers from 36 to 39,respectively,i.e.,the most refractory sulfur compounds are mainly BNT and DBT sulfur compounds with side chain substituted carbon numbers ranging from 20 to 27,which can only be removed by the hydrogenolysis route.

关 键 词：渣油加氢 硫化物 加氢脱硫 分子结构 

分 类 号：TE624[石油与天然气工程—油气加工工程]