采用水热法制备得到具有磁响应性能的碳基固体酸微球催化剂,采用扫描电镜、振动样品磁强计、X射线衍射仪、红外光谱仪、热重分析仪和Boehm滴定等手段对其进行表征,并探讨了催化剂制备条件对碳基固体酸微球催化剂催化性能的影响。结果表明:微球直径为1.1～1.3μm时,其饱和磁化强度为4.25emu/g,具有Fe3O4的特征衍射峰,且表面具有大量的酸性官能团;在磺化温度为120℃、磺化时间为8h、浓硫酸用量为15mL时,催化剂酸量达到2.84mmol/g。将催化剂应用于油酸与甲醇的酯化反应,当催化剂质量为油酸质量的7.5%,甲醇与油酸摩尔比为24∶1,酯化温度为90℃,酯化时间为3h时,酯化率达到89.43%。
Magnetic carbon-based solid acid microphere catalysts were prepared by hydrothermal method and were characterized by scanning electron microscopy,vibrating sample magnetometer,X-ray diffraction,fourier transform infrared spectroscopy,thermogravimetric analysis and Boehm titration.The effect of preparation conditions on catalytic performance of micropheres was discussed.The results showed that the diameter and saturated magnetization of microspheres were 1.1 to 1.3μm and 4.25emu/g,respectively.The characteristic diffraction peaks of ferric oxide can be observed and a large number of acid functional groups were present on the surface of micropheres.The maximum acid density was 2.84mmol/g when the sulfonation temperature 90℃,the time 8h and the amount of concentrated sulfuric acid 15mL.The as-prepared catalyst was used to catalyze the esterification reaction of oleic acid and methanol.The results showed that when the mass of the magnetic solid acid catalyst was 7.5% of oleic acid,the molar ratio of methanol to oleic acid was 24∶1,the esterification temperature 90℃ and the esterification time 3h,the esterification rate reached 89.43%.
[1] Wang L,Dong X,Jiang H,et al.Phosphorylated ordered mesoporous carbon as a novel solid acid catalyst for the esterification of oleic acid[J].Catalysis Communications,2014,56:164-167.
[2] 张文娟,马海龙,杨亚提,等.松木粉制备高比表面积炭基固体酸催化剂[J].生物质化学工程,2012,46(1):15-18.
[3] Xue W,Zhao H,Yao J,et al.Esterification of cyclohexene with formic acid over a peanut shell-derived carbon solid acid catalyst[J].Chinese Journal of Catalysis,2016,37(5):769-777.
[4] Mardhiah H H,Ong H C,Masjuki H H,et al.Investigation of carbon-based solid acid catalyst from jatropha curcas,biomass in biodiesel production[J].Energy Conversion & Management,2017,144:10-17.
[5] 齐相前,李会鹏,赵华,等.玉米粉炭基固体酸催化剂的制备及表征[J].化工新型材料,2016,44(11):163-165.
[6] Kumar V B,Pulidindi I N,Gedanken A.Selective conversion of starch to glucose using carbon based solid acid catalyst[J].Renewable Energy,2015,78:141-145.
[7] Liang X.Novel magnetic carbon based solid acid for alkylation of benzene and dodecene[J].Chemical Engineering Journal,2015,264:251-257.
[8] 陈诗渊,曾丹林,许可,等.接枝法制备磺酸基碳微球及其催化缩合反应的应用[J].现代化工,2017,37(1):88-91.
[9] 陈诗渊,曾丹林,裴阳,等.碳基固体酸微球的制备及催化性能研究[J].现代化工,2016,36(4):89-92.
[10] Deng H,Li X,Peng Q,et al.Monodisperse magnetic single-crystal ferrite microspheres[J].Angewandte Chemie,2005,44(18):2782-2785.
[11] 汪君.葡萄糖水热炭化及其活化特性研究[D].武汉:华中科技大学,2013.
[12] 娄文勇,蔡俊,段章群,等.基于纤维素的固体酸催化剂的制备及其催化高酸值废油脂生产生物柴油[J].催化学报,2011,32(11):1755-1761.
[13] Peng F,Zhang L,Wang H,et al.Sulfonated carbon nanotubes as a strong protonic acid catalyst[J].Carbon,2005,43(11):2405-2408.
基金资助
国家自然科学基金(21473126);湖北省教育厅基金(B2014094);湖北省煤转化与新型碳材料重点实验室开放基金(WKDM201506)
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