氯化咪唑基离子液体对柴油中含氮化合物选择性脱除作用研究

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通过N-甲基咪唑和烷基氯的季铵化反应合成出了咪唑环N上烷基取代基碳链长度或者饱和度不同的4种离子液体:氯化1-丁基-3-甲基咪唑(BMImCl)、氯化1-烯丙基-3-甲基咪唑(AlMImCl)、氯化1-苯甲基-3-甲基咪唑(BzMImCl)和氯化-1-辛基-3-甲基咪唑(OcMImCl)。以含咔唑(CAR)和二苯并噻吩(DBT)的甲苯-正十二烷烃溶液作为模拟柴油,测定CAR和DBT在这些离子液体中的相对分配系数,考察了离子液体对氮和硫化物的萃取脱除选择性。结果表明,在这些离子液体中CAR比DBT有更高的分配系数;4种离子液体比较,BMImCl和AlMImCl对CAR的分配系数分别达46和14,对氮和硫化合物的萃取脱除选择性SN/S分别达到125和38。测定了离子液体在模拟柴油的溶解度,发现这4种离子液体在甲苯和正十二烷烃模拟柴油中的溶解度有显著的差别,其中BMImCl和AlMImCl的溶解度相当且都很小。综合结果显示BMImCl具有最佳性能。实验还比较了BMImCl对不同碱性氮杂环化合物的萃取效果,发现其对含硫化合物和碱性含氮化合物的萃取效率随着模拟柴油中甲苯的质量分数的增加而降低,而对中性含氮化合物表现出高萃取效率,且几乎不受甲苯质量分数的影响。对一种含有361 mg·kg-1N和3598 mg·kg-1S的工业柴油,BMImCl对其对中性含氮化合物的萃取效率达到38%,而对相对含量高约十倍的含硫化合物的萃取率仅约有1.7%。综合上述结果表明,氯化1-丁基-3-甲基咪唑盐离子液体对柴油中的中性含氮化合物具有高选择性脱除作用。 Four kinds of ionic liquids with different carbon chain lengths or degrees of saturation of alkyl substituents on imidazole ring N were synthesized by quaternization of N-methylimidazole and alkyl chloride: 1-butyl-3-methyl Imidazole (BMImCl), 1-allyl-3-methylimidazolium chloride (AlMImCl), 1-benzyl-3-methylimidazolium chloride (BzMImCl) and 1-octyl-3- The base imidazole (OcMImCl). The relative partition coefficients of CAR and DBT in these ionic liquids were determined by using toluene and n-dodecane solution containing carbazole (CAR) and dibenzothiophene (DBT) as simulated diesel. The effects of ionic liquids on nitrogen and sulfide Selective removal of the extract. The results showed that CAR had a higher partition coefficient than DBT in these ionic liquids. The distribution coefficients of BMImCl and AlMImCl to CAR were 46 and 14, respectively, for the four ionic liquids, and the selectivity for nitrogen and sulfur compounds was removed / S to 125 and 38, respectively. The solubility of the ionic liquid in the simulated diesel was measured and found that the solubility of the four ionic liquids in toluene and n-dodecane simulated diesel were significantly different. The solubility of BMImCl and AlMImCl was quite small and both were very small. The combined results show that BMImCl has the best performance. The experiment also compared the extraction efficiency of BMImCl with different basic nitrogen heterocyclic compounds and found that the extraction efficiency of sulfur compounds and basic nitrogen compounds decreased with the increase of the mass fraction of toluene in simulated diesel, Nitrogen-containing compounds exhibit high extraction efficiencies with little effect on the toluene mass fraction. For a commercial diesel containing 361 mg · kg-1N and 3598 mg · kg-1S, BMImCl achieved an efficiency of 38% for its neutral nitrogen-containing compounds and about 10 times the relative content of sulfur-containing compounds The extraction rate is only about 1.7%. The above results show that 1-butyl-3-methylimidazolium chloride ionic liquid has high selective removal of neutral nitrogen compounds in diesel oil.
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