Synthesis of HeteroplyacidInioc Liquids and Their Application in Clean Oxidation

doi:10.3969/j.issn.1006-396X.2015.06.003

Journal of Petrochemical Universities ›› 2015, Vol. 28 ›› Issue (6): 14-19.DOI: 10.3969/j.issn.1006-396X.2015.06.003

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Synthesis of HeteroplyacidInioc Liquids and Their Application in Clean Oxidation

（1.Division of Chemistry, Chemical Engineering and Environment, Liaoning Shihua University, Fushun Liaoning 113001, China;[ＪＰ]　 2. School of Environmental and Chemical Engineering, Tianjin Polytechnic University, Tianjin 300387, China)

Received:2015-01-09 Revised:2015-09-08 Published:2015-12-25 Online:2015-12-07

杂多酸型离子液体的合成及在清洁氧化中的应用

宁建梅¹, 彭坤¹, 杨丽霞¹, 李艺², 桂建舟^{1, 2}, 刘道胜¹, 吕振波¹

( 1. 辽宁石油化工大学化学化工与环境学部, 辽宁抚顺1 1 3 0 0 1; 2. 天津工业大学环境与化学工程学院, 天津3 8 0 3 8 7)

通讯作者: 吕振波( 1 9 6 4 - ) , 男, 博士, 教授, 从事催化反应工程、石油化学品方面研究; E - m a i l : l z h b 6 6 8 4 7 0 8@1 6 3. c o m。
作者简介:宁建梅( 1 9 8 7 - ) , 女, 硕士研究生, 从事催化氧化脱硫方面研究; E - m a i l : n j m 0 6 0 7@1 6 3. c o m。
基金资助:
国家自然科学基金( 2 1 1 0 3 0 7 7) ; 辽宁自然科学基金资助项目( 2 0 1 2 0 2 1 2 3) ; 新世纪优秀人才支持计划( NC E T - 1 1 -
1 0 1 1) ; 辽宁省优秀人才支持计划( L R 2 0 1 0 2 4, L J Q 2 0 1 1 0 3 5) 。

Abstract

Abstract: Heteropoly acid type ionic liquid BMAI［HPW12O40］ was synthesized as catalyst for simulate diesel oxidative desulfurization which was characterized by 1HNMR,13CNMR,IR and TG. The optimal reaction conditions were as follows: reaction temperature of 40 ℃, 15 mL oil sample, 1.75 mL hydrogen peroxide and 0.028 g heteropoly acid type ionic liquid. Under this conditions, good desulfurization ratio (95.5%) can be achieved. After the reaction, diesel oil and catalyst can be separated by simple decantation, and the activity of catalysts would not change obviously after recycling for 5 times. Furthermore, the oxidation kinetics of 4,6dimethyldibenzothiophen was investigated. The oxidation of 4,6DMDBT can be treated as a firstorder reaction, with the apparent activation energy Ea 31.55 kJ/mol and the preexponential factor K0 2.36×104 min-1.

Key words: Phosphotungstic acid ionic liquid, , Catalytic oxidation desulphurization, , Simulated oil, , Oxidation kinetics

摘要： 合成了杂多酸型离子液体BMA I [ HPW1 2O4 0] , 并对其进行了核磁共振波谱( 1H - NMR、 1 3C - NMR) 、红外光谱( I R) 和热重分析技术( TG) 等表征, 将其作催化剂用于模拟柴油氧化脱硫。结果表明, 在4 0℃、 1 5mL油样、 1. 7 5mLH2O2、 0. 0 2 8g离子液体的条件下, 4, 6 - 二甲基二苯并噻吩( 4, 6 - DMD B T) 的脱硫率可达到9 5. 5%; 催化剂重复使用5次之后, 催化活性基本不变; 同时对4, 6 - 二甲基二苯并噻吩的反应动力学进行了研究, 得知该反应为一级反应, 表观活化能Ea 为3 1. 5 5k J /m o l , 指前因子K0 为2. 3 6×1 0 4 m i n-1。

关键词: 磷钨酸离子液体, 催化氧化脱硫, 模拟油, , 反应动力学

Ning Jianmei,Peng Kun,Yang Lixia,et al. Synthesis of HeteroplyacidInioc Liquids and Their Application in Clean Oxidation[J]. Journal of Petrochemical Universities, 2015, 28(6): 14-19.

宁建梅, 彭坤, 杨丽霞, 李艺, 桂建舟, 刘道胜, 吕振波. 杂多酸型离子液体的合成及在清洁氧化中的应用[J]. 石油化工高等学校学报, 2015, 28(6): 14-19.

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Synthesis of HeteroplyacidInioc Liquids and Their Application in Clean Oxidation

杂多酸型离子液体的合成及在清洁氧化中的应用

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