超临界甲醇中氧化脱除模型物中噻吩硫的研究  

Removal of thiophene from model compounds by oxidation in supercritical methanol

作　　者：陈圣 陈辉[2] 许金山[3] 许晓斌[3] 许军 曹发海[1] CHEN Sheng;CHEN Hui;XU Jin-shan;XU Xiao-bin;XU Jun;CAO Fa-hai(Engineering Research Center of Large-Scale Reactor Engineering and Technology of Ministry of Education,Department of Chemical Engineering,East China University of Science and Technology,Shanghai 200237,China;SINOPEC,Beijing 100728,China;Research Institute of SINOPEC Qilu Branch,Zibo 255400,China)

机构地区：[1]华东理工大学大型工业反应器工程教育部工程研究中心,上海200237 [2]中国石油化工股份有限公司,北京100728 [3]中石化齐鲁分公司研究院,山东淄博255400

出　　处：《高校化学工程学报》2020年第3期639-647,共9页Journal of Chemical Engineering of Chinese Universities

摘　　要：传统加氢脱硫往往难以脱除重油中的噻吩类硫化物。利用噻吩类硫化物氧化后的极性增加,在超临界甲醇条件下强化其在极性溶剂中的溶解度,可深度脱除重油中的噻吩硫。以二苯并噻吩(DBT)与十四烷为模型油,甲醇为超临界介质,考察了无催化时反应条件对超临界氧化脱硫性能的影响,不同催化氧化体系的脱硫效率。利用红外光谱、气相色谱-质谱联用对反应产物进行分析以研究脱硫机理。结果表明,在无催化时,反应温度260℃、反应压力8.5~9.0 MPa、反应时间3 h、过氧化二叔丁基作氧化剂且氧硫摩尔比为3:1时,噻吩模型物的脱硫率最高,达42%。在催化氧化体系中,催化剂用量与硫的摩尔比为1:10时催化剂使用效率最高,3种脱硫效果较好的催化氧化体系脱硫率分别达到了47%、45%、45%。FTIR、GC-MS结果表明二苯并噻吩被氧化为相应亚砜并转移至甲醇相,从而实现了硫化物的脱除。Thiophenic sulfur is the main sulfide in residue oil,which is difficult to be removed by traditional hydrodesulfurization.Supercritical oxidative desulfurization was proposed in this study.Dibenzothiophene(DBT) and tetradecane were used as model oil and methanol as supercritical medium,and the effects of reaction conditions on the performance of oxidative desulfurization in supercritical methanol and desulfurization efficiency of different catalytic oxidation systems were investigated.The reaction products were analyzed by infrared spectroscopy and gas chromatography-mass spectrometry to study the desulfurization mechanism.The results show that the desulfurization efficiency reaches the highest without catalyst when the reaction temperature=260℃,the reaction pressure=8.5~9.0 MPa,the reaction time=3 h,the di-ter=-butyl peroxide is the oxidant and the molar ratio of oxygen to sulfur=3:1.With catalytic oxidation systems,the desulfurization efficiency of thiophene model compound achieves the highest when the molar ratio of catalyst dosage to sulfur=1:10.Three catalytic oxidation systems achieved relatively high desulfurization efficiency of 47%,45% and45% respectively.FTIR and GC-MS results show that dibenzothiophene is oxidized to corresponding sulfoxide and transferred to methanol phase and removed.

关 键 词：超临界甲醇 氧化脱硫 二苯并噻吩 正十四烷 模型物 

分 类 号：TE991.1[石油与天然气工程—石油机械设备]