相转移催化氧化-萃取脱除直馏柴油中硫化物的研究  

STUDY ON OXIDATION-EXTRACTION DESULFURIZATION OF STRAIGHT-RUN DIESEL BY PHASE TRANSFER CATALYSIS

作　　者：佘林源[1] 颜家保[1] 童俊[2] 

机构地区：[1]湖北省煤转化与新型炭材料重点实验室,武汉430081 [2]武钢股份有限公司

出　　处：《石油炼制与化工》2008年第7期5-9,共5页Petroleum Processing and Petrochemicals

摘　　要：以四丁基溴化铵(TBAB)为相转移剂,采用 H_2O_2-HCOOH 催化氧化直馏柴油中含硫化合物,利用 N,N-二甲基甲酰胺(DMF)萃取脱除含硫化合物。通过考察 TBAB 用量、反应温度、反应时间、H_2O_2和 HCOOH 用量、剂油比、搅拌速率对柴油脱硫效果的影响,确定适宜的操作条件为:w(TBAB)=0.10%,反应温度60℃,反应时间2.0 h,V(H_2O_2)/V(柴油)为10%,V(H_2O_2)/V(HCOOH)=1:2,剂油体积比2:5,搅拌速率150r/min。在该反应条件下,直馏柴油的脱硫率达到82.03%,柴油收率为92.02%。模拟柴油脱硫反应动力学研究结果表明,H_2O_2-HCOOH 相转移催化氧化脱除噻吩硫反应为表观一级反应,活化能为7.47 kJ/mol。The desulfurization of straight-run diesel fuel was carried out in a hydroperoxideformic acid catalytic oxidation system using tetrabutylammonium bromide（TBAB）as phase transfer catalyst, and later the oxidized organic sulfur compounds were separated by N, N Dimethylformamide （DMF）extraction. The influences of the amount of TBAB,reaction temperature,reaction time,dosages of hydroperoxide and formic acid,the volume ratio of solvent-to-oil and mixing speed on the desulfurization of straight run diesel fuel were investigated. The optimum operation conditions were obtained as follows： a TBAB content of 0. 1%, a reaction temperature of 60 ℃,a reaction time of 2 h, a volume ratio of hydroperoxide to-diesel of 0.1,a volume ratio of hydroperoxide-to-formic acid of 0.5,a volume ratio of extractant to diesel of 0.4 and a mixing speed of 150 r/min. Under such conditions the removal rate of sulfur and the recovered yield of diesel oil were 82.03% and 92.02% ,respectively, The results of kinetics study by model fuel showed that the reaction of thiophene removal by H202-HCOOH phase transfer catalytic oxidation system was a pseudo first order reaction with an activation energy of 7.47 kJ/mol.

关 键 词：柴油 氧化反应 脱硫 相转移催化剂 动力学 

分 类 号：TE624.55[石油与天然气工程—油气加工工程]