Synthesis of poly (ionic liquid) s solid acid catalyst and its catalytic performance in glycerol acetylation

doi:10.16085/j.issn.1000-6613.2017-0104

Abstract

Abstract: A functional poly (ionic liquid) s (PILs) solid acid catalyst was prepared through free radical copolymerization of ionic liquids precursor and the subsequent protonation and ion-exchange with concentrated sulfuric acid.The as-prepared acidic catalyst was characterized by FTIR,SEM,TEM,XPS,TGA,elemental analysis and potentiometric titration.It was found that the acid PILs had a multi-layer microstructure with favorable thermal stability and high Brønsted acid site density.Its performance was evaluated in the acetylation of glycerol without any water-carrying agent.It exhibited high catalytic activity and selectivity.Glycerol conversion of 98.2%,monoacetin selectivity of 11.6% and total diacetin and triacetin selectivity of 88.4% were obtained under the optimum reaction conditions of n(acetic acid):n(glycerol)=6,catalyst dosage=4% of glycerol,120℃,4h.The catalytic performance was better than that using Amberlyst-15.The PILs solid acid catalyst was easily recovered and had good hydrothermal stability.A further exchanging of used PILs with H₂SO₄ could make the catalyst restore its catalytic performance and it could be reused for 4 times.

Key words: catalyst, polymerization, ionic liquids, selectivity, glycerol, acetylation

摘要： 通过自由基共聚，质子化及离子交换两步法合成聚咪唑基离子液体固体酸催化剂（PILs）。采用傅里叶红外光谱（FTIR）、扫描电镜（SEM）、透射电镜（TEM）、X射线光电子能谱分析（XPS）、热重分析（TGA）、元素分析和电位滴定的方法对该催化剂的结构和性能进行了表征。结果表明该催化剂具有层状结构、良好的热稳定性和较高的质子酸浓度，并在不加入带水剂的条件下，考察了该聚离子液体固体酸催化剂对甘油乙酰化反应的催化作用。结果表明该PILs固体酸催化剂具有良好的选择催化活性，在酸醇摩尔比为6：1、催化剂用量4%（质量分数）、120℃、4h的最优条件下，甘油转化率达98.2%，单乙酸甘油酯的选择性为11.6%，二乙酸甘油酯和三乙酸甘油酯的总选择性高达88.4%，优于Amberlyst-15的催化效果。该催化剂易回收，具有良好的水热稳定性，且重复使用4次经再生后仍能保持良好的选择催化活性。

关键词: 催化剂, 聚合, 离子液体, 选择性, 甘油, 乙酰化

CLC Number:

TQ032.4

ZHANG LÜhong, WANG Ruijin, JIANG Bin, SUN Yongli, YANG Huawei. Synthesis of poly (ionic liquid) s solid acid catalyst and its catalytic performance in glycerol acetylation[J]. Chemical Industry and Engineering Progress, 2017, 36(07): 2497-2503.

张吕鸿, 王瑞瑾, 姜斌, 孙永利, 杨华伟. 聚离子液体固体酸催化剂的制备及催化甘油乙酰化性能[J]. 化工进展, 2017, 36(07): 2497-2503.

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