焦化汽柴油中苯酚、苯硫酚类化合物对比分析及其来源探讨  

COMPARATIVE ANALYSIS AND ORIGINATION OF PHENOL AND THIOPHENOL DERIVATIVES IN COKER NAPHTHA AND DIESEL

作　　者：赵悦[1] 李飞[1] 宫红[1] 姜恒[1] Zhao Yue Li Fei Gong Hong Jiang Heng(School of Chemical and Material Science, Liaoning Shihua University, Fushun, Liaoning 113001)

机构地区：[1]辽宁石油化工大学化学与材料科学学院,辽宁抚顺113001

出　　处：《石油炼制与化工》2017年第5期15-20,共6页Petroleum Processing and Petrochemicals

基　　金：国家自然科学基金资助项目(21171083)

摘　　要：采用NaOH质量分数20%的液碱对不同产地(或来源)的焦化汽油和焦化柴油进行抽提,得到可提取酸性物,采用气相色谱-质谱联用(GC-MS)技术对可提取酸性物进行分析,结果表明:焦化汽油中可提取酸性物除苯酚类化合物外,还含有苯硫酚类化合物以及少量小分子硫醚;与焦化汽油不同的是,焦化柴油中的可提取酸性物几乎全部是苯酚类化合物。不同产地的焦化汽油中苯硫酚质量分数(y)与对应的减压渣油硫质量分数(x)呈线性关系y=0.04x-0.005 06(R^2=0.999);焦化汽油的苯硫酚类化合物含量越高,其室温储存安定性越差;碱洗后的焦化汽油其室温储存安定性大幅提高;酚类化合物的来源可能与延迟焦化过程中芳基醚中醚键的断裂以及芳香酸的氧化脱羧等化学反应有关,而苯硫酚类化合物可能来自于苯酚类化合物与H_2S的高温反应。The extractable acidic compounds were obtained by extracting delayed coking naphtha and diesel from different sources with 20% NaOH.These extractable acidic compounds were analyzed by gas chromatography-mass spectrometry（GC-MS）.The results show that the extractable acidic compounds in coker naphtha contain thiophenols and small molecule thiols in addition to phenols.Differs from coker naphtha,almost all extractable acidic compounds in coker diesel are phenols.Excellent linearity between the thiophenols content（y）in coker naphtha and the sulfur content（x）in the corresponding vacuum residue feedstock is observed[y =0.04x-0.005 06（R^2=0.999）].The higher content of thiophenols in coker naphtha,the worse its storage stability at room temperature.The stability of the coker naphtha is greatly improved after caustic wash.The origin of phenols may be related to the hydrolysis of aryl ether bond and the oxidative decarboxylation of aromatic acids in the delayed coking process.The thiophenols may come from the reaction of the phenols with H_2S at high temperature.

关 键 词：焦化汽油 焦化柴油 苯酚类化合物 苯硫酚类化合物 

分 类 号：TE626.2[石油与天然气工程—油气加工工程]