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第 36 卷第 1 期 精 细 化 工 Vol.36, No.1
201 9 年 1 月 FINE CHEMICALS Jan. 2019

催化与分离提纯技术
Ce 改性硅钨酸催化制备月桂酸单甘酯

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朱广琪 ，李佳敏 ，张晓芳 ，韩晓祥 ，
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唐秀娟 ，王奎武 ，王彦波
（1. 浙江工商大学 食品与生物工程学院，浙江 杭州 310018；2. 浙江工商大学 环境科学与工程学院，
浙江 杭州 310018）
摘要：采用离子交换法合成多种稀土改性硅钨酸催化剂 M x H 4–3x SiW 12 O 40 （M = La, Ce, Pr, Nd, Sm; x = 1/3, 2/3, 1,
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4/3），并利用 FTIR、XRD、TGA-DTG、固体核磁共振结合探针分子技术（ P-TMPO MAS-NMR）对
Ce x H 4–3x SiW 12 O 40 结构、稳定性及酸性进行了表征；结果表明，Ce 1/3 H 3 SiW 12 O 40 催化剂在月桂酸单甘酯制备中显
示出最好的催化性能。稀土 Ce 有效结合到硅钨酸上，制备的催化剂保持了完整的 Keggin 结构。与纯硅钨酸相
比，Ce x H 4–3x SiW 12 O 40 的酸强度有所减弱，但由于该类催化剂较强的 Brønsted 酸性及 Brønsted-Lewis 酸性位间
的协同效应，使 Ce x H 4–3x SiW 12 O 40 在月桂酸单甘酯的制备中具有良好的催化性能。以 Ce 1/3 H 3 SiW 12 O 40 为催化剂，
在甘油/月桂酸物质的量比为 4、催化剂用量为月桂酸质量的 4%、反应温度 423 K、反应时间 120 min 下，月桂
酸单甘酯产率为 78.4%；动力学研究表明，该反应活化能为 42.37 kJ/mol；Ce 1/3 H 3 SiW 12 O 40 催化剂经 5 次回收利
用后，月桂酸单甘酯的产率为 71.4%，具有较好的重复使用性能。
关键词：稀土；硅钨酸；酯化反应；月桂酸单甘酯；催化技术
中图分类号：O643.32 文献标识码：A 文章编号：1003-5214 (2019) 01-0074-08

Preparation of Glycerol Monolaurate by Cerium

Modified Tungstosilicic Acid Catalysts

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ZHU Guang-qi , LI Jia-min , ZHANG Xiao-fang , HAN Xiao-xiang ,
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TANG Xiu-juan , WANG Kui-wu , WANG Yan-bo
（1. School of Food Science and Biotechnology, Zhejiang Gongshang University, Hangzhou 310018, Zhejiang, China; 2.
School of Environmental Science and Engineering, Zhejiang Gongshang University, Hangzhou 310018, Zhejiang,
China）
Abstract: A series of rare earth elements modified tungstosilicic acid catalysts M xH 4–3xSiW 12O 40 (M=La,
Ce, Pr, Nd, Sm; x=1/3, 2/3, 1, 4/3) were prepared by ion exchange method. The structure, stability and
acidity of Ce xH 4-3xSiW 12O 40 catalysts were characterized by FTIR, XRD, TGA-DTG and solid-state
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P-TMPO MAS-NMR spectra of adsorbed trimethylphosphine oxide ( P-TMPO MAS-NMR). The results
showed that Ce 1/3H 3SiW 12O 40 catalyst had the best catalytic activity in the synthesis of glycerol monolaurate
(GML). Rare earth element cerium effectively bound to tungstosilicic acid, which made the prepared
catalyst maintain a complete Keggin structure. Although the acidity of Ce x H 4–3x SiW 12 O 40 catalysts decreased
compared with that of tungstosilicic acid, the catalysts exhibited good catalytic activities during the
esterification due to strong Brønsted acidity and Brønsted-Lewis acid synergy. When the molar ratio of
glycerol (GL) to lauric acid (LA) was 4.0, the mass fraction of Ce 1/3H 3SiW 12O 40 catalyst was 4% (based on
LA), the reaction temperature was 423 K, and the reaction time was 120 min, the yield of GML was 78.4%.
Kinetic studies revealed that the apparent activation energy of the reaction was 42.37 kJ/mol. The yield of
GML could still reach 71.4% after Ce 1/3H 3SiW 12O 40 catalyst was reused for 5 times, indicating that this
catalyst had excellent reuse ability.
Key words: rare earth; tungstosilicic acid; esterification; glycerol monolaurate; catalysis technique

收稿日期：2018-03-15; 定用日期：2018-06-11; DOI: 10.13550/j.jxhg.20180171
作者简介：朱广琪(1993—)，女，硕士生。联系人：韩晓祥(1974—)，男，副研究员，硕士生导师，电话：0571-28008975，
E-mail：hxx74@126.com；王彦波(1978—)，男，教授，博士生导师，电话：0571-28008963，E-mail：wyb1225@163.com。