Oxidative Desulfurization of Fuel Oil with H_(3)PO_(4)-based Deep Eutectic Solvents

作     者：Li Xiuping Zhang Jiayin Hou Liangpei Zhao Rongxiang Li Xiuping;Zhang Jiayin;Hou Liangpei;Zhao Rongxiang

作者机构：School of Petrochemical EngineeringLiaoning Petrochemical UniversityFushun 113001China 

出 版 物：《China Petroleum Processing & Petrochemical Technology》 (中国炼油与石油化工（英文版）)

年 卷 期：2024年第26卷第2期

页      面：178-186页

核心收录：

学科分类：081702[工学-化学工艺] 08[工学] 0817[工学-化学工程与技术] 

基　　金：the College Student Innovation and Entrepreneurship Training Program Project of Liaoning Province(202310148016) Doctoral Fund of Liaoning Province(201501105) 

主　　题：deep eutectic solvents phosphoric acid zinc chloride oxidative desulfurization 

摘      要：A series of Lewis-acid deep eutectic solvents (DESs) were synthesized by stirring phosphoric acid and zincchloride as raw materials at 80℃ to form H_(3)PO_(4)/nZnCl_(2) (n = 0.1, 0.25, 0.5, 0.75, 1). The DESs were characterized byFourier transform infrared spectrophotometry (FT-IR), thermogravimetry/differential thermogravimetry (TG/DTG), andelectron spray ionization mass spectrometry (ESI-MS). The DESs were used as both extractants and catalysts to removedibenzothiophene from fuels via oxidative desulfurization (ODS). Experiments were performed to investigated the influenceof factors such as composition of DES, temperature, oxidant dosage (molar ratio of O:S), DES dosage (volume ratio ofDES:oil), and number of cycles on desulfurization rate. The results indicated that the removal rate of dibenzothiophene (DBT)was affected by the Lewis acidic DESs, with that of H_(3)PO_(4)/0.25∙ZnCl_(2) reaching 96.4% under optimal conditions (Voil=5 mL,VDES=1 mL, an oxidant dosage of 6, T=50 ℃). After six cycles, the desulfurization rate of H_(3)PO_(4)/0.25∙ZnCl_(2) remained above94.1%. The apparent activation energy of dibenzothiophene (DBT) removal reaction was determined by a pseudo-first orderkinetic equation according to the Arrhenius equation to be 32.34 kJ/mol, as estimated. A reaction mechanism is proposedbased on the experimental data and characterization results.