聚离子液体固体酸催化剂的制备及催化甘油乙酰化性能

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

摘要/Abstract

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

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

中图分类号:

TQ032.4

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.

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.

参考文献

[1] SANI Y M,DAUD W M A W,AZIZ A R A. Activity of solid acid catalysts for biodiesel production:a critical review[J]. Applied Catalysis A:General,2014,470:140-161.
[2] 鲁厚芳,史国强,刘颖颖,等. 生物柴油生产及性质研究进展[J]. 化工进展,2011,30(1):126-136. LU H F,SHI G Q,LIU Y Y,et al. A review on researches on biodiesels production and their properties[J]. Chemical Industry and Engineering Progress,2011,30(1):126-136.
[3] MODIBA E,ENWEREMADU C,RUTTO H. Production of biodiesel from waste vegetable oil using impregnated diatomite as heterogeneous catalyst[J]. Chinese Journal of Chemical Engineering,2015,23(1):281-289.
[4] BHANDARI K,CHAURASIA S P,DALAI A K. Lipase-catalyzed esterification of docosahexaenoic acid-rich fatty acids with glycerol[J]. Chemical Engineering Communications,2015,202(7):920-926.
[5] ZHOU Z M,LI X,ZENG T Y,et al. Kinetics of hydrogenolysis of glycerol to propylene glycol over Cu-ZnO-Al₂O₃ catalysts[J]. Chinese Journal of Chemical Engineering,2010,18(3):384-390.
[6] GROSS M S,SANCHEZ B S,QUERINI C A. Glycerol oxidation in liquid phase:highly stable Pt catalysts supported on ion exchange resins[J]. Applied Catalysis A:General,2015,501:1-9.
[7] SERETIS A,TSIAKARAS P. Hydrogenolysis of glycerol to propylene glycol by in situ produced hydrogen from aqueous phase reforming of glycerol over SiO₂-Al₂O₃ supported nickel catalyst[J]. Fuel Processing Technology,2016,142:135-146.
[8] 周维,赵玉军,马新宾. 高活性Cu/SiO₂催化剂上甘油氢解制1,2-丙二醇[J]. 化工学报,2015,66(8):2999-3006. ZHOU W,ZHAO Y J,MA X B. Continuous hydrogenolysis of glycerol to 1,2-propanediol on highly active Cu/SiO₂ catalysts[J]. CIESC Jorunal,2015,66(8):2999-3006.
[9] GORJI Y M,GHAZIASKAR H S. Optimization of solketalacetin synthesis as a green fuel additive from ketalization of monoacetin with acetone[J]. Industrial & Engineering Chemistry Research,2016,55(25):6904-6910.
[10] RAHMAT N,ABDULLAH A Z,MOHAMED A R. Recent progress on innovative and potential technologies for glycerol transformation into fuel additives:a critical review[J]. Renewable & Sustainable Energy Reviews,2010,14(3):987-1000.
[11] MELERO J A,VICENTE G,PANIAGUA M,et al. Etherification of biodiesel-derived glycerol with ethanol for fuel formulation over sulfonic modified catalysts[J]. Bioresource Technology,2012,103(1):142-151.
[12] HASABNIS A,MAHAJANI S. Entrainer-based reactive distillation for esterification of glycerol with acetic acid[J]. Industrial & Engineering Chemistry Research,2010,49(19):9058-9067.
[13] 王婷,蔡文静,刘熠斌,等. 固体酸催化制备生物柴油研究进展[J].化工进展,2016,35(9):2783-2789. WANG T,CAI W J,LIU Y B,et al. Research progress in preparation of biodiesel with solid acid catalyst[J]. Chemical Industry and Engineering Progress,2016,35(9):2783-2789.
[14] REZAYAT M,GHAZIASKAR H S. Continuous synthesis of glycerol acetates in supercritical carbon dioxide using Amberlyst 15(R)[J]. Green Chemistry,2009,11(5):710-715.
[15] ZHOU L M,NGUYEN T H,ADESINA A A. The acetylation of glycerol over Amberlyst-15:kinetic and product distribution[J]. Fuel Processing Technology,2012,104:310-318.
[16] ZHOU L M,AL-ZAINI E,ADESINA A A. Catalytic characteristics and parameters optimization of the glycerol acetylation over solid acid catalysts[J]. Fuel,2013,103:617-625.
[17] GONCALVES V L C,PINTO B P,SILVA J C,et al. Acetylation of glycerol catalyzed by different solid acids[J]. Catalysis Today,2008,133:673-677.
[18] DIAZ I,MARQUEZ-ALVAREZ C,MOHINO F,et al. Combined alkyl and sulfonic acid functionalization of MCM-41-type silica-Part 2. Esterification of glycerol with fatty acids[J]. Journal of Catalysis,2000,193(2):295-302.
[19] TREJDA M,STAWICKA K,DUBINSKA A,et al. Development of niobium containing acidic catalysts for glycerol esterification[J]. Catalysis Today,2012,187(1):129-134.
[20] SUN Z,DUAN X X,TAO M L,et al. Design of a highly efficient indium-exchanged heteropolytungstic acid for glycerol esterification with acetic acid[J]. Catalysis Surveys from Asia,2016,20(2):82-90.
[21] 杨雪娇,方岩雄,张焜,等. 基于可聚合离子液体的功能高分子材料研究进展[J]. 化工进展,2015,34(7):1919-1927. YANG X J,FANG Y X,ZHANG K,et al. Progress of polymerizable ionic liquids-based functional polymers[J]. Chemical Industry and Engineering Progress,2015,34(7):1919-1927.
[22] YUAN J Y,MECERREYES D,ANTONIETTI M. Poly(ionic liquid)s:an update[J]. Progress in Polymer Science,2013,38(7):1009-1036.
[23] XIN Q P,LI Z,LI C D,et al. Enhancing the CO₂ separation performance of composite membranes by the incorporation of amino acid-functionalized graphene oxide[J]. Journal of Materials Chemistry A,2015,3(12):6629-6641.
[24] 赵薇,贺高红,刘红晶,等. 离子液体二氧化碳分离膜研究进展[J]. 化工进展,2014,33(12):3292-3298,3308. ZHAO W,HE G H,LIU H J,et al. Developments in ionic liquid membranes for CO₂ separation[J]. Chemical Industry and Engineering Progress,2014,33(12):3292-3298,3308.
[25] LIU C G,WANG S,ZHOU H,et al. Thermoresponsive poly(ionic liquid):controllable RAFT synthesis,thermoresponse,and application in dispersion RAFT polymerization[J]. Journal of Polymer Science Part A-Polymer Chemistry,2016,54(7):945-954.
[26] HE C E,SUN S,PENG H Y,et al. Poly(ionic liquid)-assisted reduction of graphene oxide to achieve high-performance composite electrodes[J]. Composites Part B-Engineering,2016,106:81-87.
[27] WANG X C,LI J,CHEN G J,et al. Hydrophobic mesoporous poly(ionic liquid)s towards highly efficient and contamination-resistant solid-base catalysts[J]. ChemCatChem,2015,7(6):993-1003.
[28] ZHANG J,ZHANG S J,HAN J X,et al. Uniform acid poly ionic liquid-based large particle and its catalytic application in esterification reaction[J]. Chemical Engineering Journal,2015,271:269-275.