Oxidative desulfurization of fuel catalyzed by metal-based surfactant-type ionic liquids
Oxidative desulfurization of fuel catalyzed by metal-based surfactant-type ionic liquids
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DOI：
10.1016/j.molcata.2011.07.002
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发表时间：
2011-08
影响因子：
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通讯作者：
Wenshuai Zhu;G. Zhu;Hua-ming Li;Y. Chao;Yonghui Chang;Guangying Chen;C. Han
中科院分区：
文献类型：
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作者：
Wenshuai Zhu;G. Zhu;Hua-ming Li;Y. Chao;Yonghui Chang;Guangying Chen;C. Han
合成并表征了金属基表面活性剂型离子液体（MSIL）甲基三辛基铵过氧钼酸盐[（CH3）N（n-C8H17）3] 2Mo2O11和过氧钨酸盐[（CH3）N（n-C8H17）3] 2W2O11。本文将MSIL应用于H2O2脱除含硫化合物，并具有反应诱导自分离催化特性。考察了H2O2/DBT（摩尔比）、油/MSIL（质量比）和搅拌速率对[（CH3）N（n-C8H17）3] 2Mo2O11催化脱硫体系的影响，确定了最佳反应条件。季铵盐阳离子在反应条件下可将催化活性物种转移到芳香族含硫化合物上，获得较高的氧化反应速率。动力学实验表明，氧化脱硫反应符合准一级动力学，并计算了反应速率常数和半衰期。不同底物的氧化活性大小顺序为：DBT> 4，6-DMDBT> BT。MSIL [（CH3）N（n-C8H17）3] 2Mo2O11可循环使用10次，活性略有下降。[（CH3）N（n-C8H17）3] 2Mo2O11在不同溶剂中对含硫化合物的脱除也有较好的催化效果。多反应氧化脱硫工艺对预加氢汽油是可行和有效的。
Metal-based surfactant-type ionic liquids (MSILs) methyltri-n-octylammonium peroxomolybdate [(CH3)N(n-C8H17)3]2Mo2O11and peroxotungstate [(CH3)N(n-C8H17)3]2W2O11were synthesized and characterized, which have been extended to new families and generations of functionalized ILs. Here the MSILs were applied in removal of sulfur-containing compounds with H2O2and possessed of the character of reaction-induced self-separation catalysis. The effects of H2O2/DBT (molar ratio), oil/MSIL (mass ratio) and the agitation rate were studied to estimate the optimal conditions for the desulfurization system catalyzed by [(CH3)N(n-C8H17)3]2Mo2O11. The quaternary ammonium cation could transfer the catalytic active species to the aromatic sulfur compounds under the reaction conditions and higher oxidative reaction rate was achieved. Kinetic experiments revealed that the oxidative desulfurization reaction was in accordance with pseudo-first-order kinetics and the reaction rate constant and half-life were calculated. Furthermore, the oxidation reactivity of different substrates was in the following order: DBT>4,6-DMDBT>BT. The MSIL [(CH3)N(n-C8H17)3]2Mo2O11could be recycled for 10-times with a slight decrease in activity. [(CH3)N(n-C8H17)3]2Mo2O11was also an efficient catalyst to remove the sulfur-containing compound in different solvents. Multiple reactions of oxidation desulfurization process were feasible and effective for prehydrotreated gasoline.