Heterogeneous aldol condensation catalyzed with Pickering emulsion

doi:10.11949/0438-1157.20221196

Abstract

Abstract:

In recent years, the coal-based synthesis of methyl methacrylate (MMA) process has received extensive attention. However, the aldol condensation reaction of formaldehyde and propionaldehyde has bottleneck problems such as discontinuous reaction process and complicated separation and recovery process. A reinforced water-in-oil (W/O) Pickering emulsion was constructed with surface-modified silica (SiO₂) nanospheres used as stabilizers and the emulsifier particles were further “reinforced” by cross-linking to form a dense SiO₂ shell layer around the droplets. This Pickering emulsion system not only achieves the “solid loading” of the catalyst and the heterogeneous mild conversion of the aldol condensation reaction process, but also provides opportunities for other homogeneous catalytic reaction systems.

Key words: emulsion, multiphase reaction, catalysis, methacrolein, porous microspheres

摘要：

近年来，煤基合成甲基丙烯酸甲酯(MMA)工艺获得广泛关注，但甲醛、丙醛羟醛缩合反应存在反应过程不连续、分离回收过程复杂等瓶颈问题。本文以表面改性的二氧化硅(SiO₂)纳米球为乳化剂，乳化剂颗粒交联进一步“加固”，在液滴周围形成了致密SiO₂壳层，构筑了强化型油包水(W/O)Pickering乳液。该Pickering乳液催化体系不仅实现了催化剂的“固载”和羟醛缩合温和反应过程的非均相转化，也为其他均相催化反应体系提供了机遇。

关键词: 乳液, 多相反应, 催化, 甲基丙烯醛, 多孔微球

CLC Number:

TQ 032.4

Yu CHEN, Xiaoyan ZHENG, Hui ZHAO, Erqiang WANG, Jie LI, Chunshan LI. Heterogeneous aldol condensation catalyzed with Pickering emulsion[J]. CIESC Journal, 2023, 74(1): 449-458.

陈余, 郑晓妍, 赵辉, 王二强, 李杰, 李春山. Pickering乳液催化非均相羟醛缩合反应研究[J]. 化工学报, 2023, 74(1): 449-458.

Figures/Tables 13

Fig.1 Reaction route of MMA production with coal-based ethylene/syngas

Fig.2 Schematic illustration of Pickering emulsion preparation and fixed-bed continuous catalytic reaction process

Fig.3 The contact angle of SiO2 particles modified with various MTMS contents and the microscope image of Pickering emulsions stabilized by different amounts of MTMS-modified SiO2

Fig.4 FT-IR spectra of SiO2 particles modified with different contents of MTMS

Fig.5 The diameter of droplets with the different stabilizer content and the optical microscope images of Pickering emulsions with varied stabilizer contents

Fig.6 Optical microscope images of the reinforced Pickering emulsion prepared by different crosslinking agents and various cross-linking methods

Fig.7 SEM images of porous microspheres

Fig.8 The N2 adsorption-desorption isotherms and BJH pore size distribution of porous microspheres

Table 1 Characterization of the pore structure of porous microspheres with different crosslinker contents

样品	BET表面积/ （m²·g^-1）	孔径/nm	孔体积/ （cm³·g^-1）
P2	290	10.6	0.66
P4	280	8.7	0.66
P8	291	9.3	0.66
P10	449	8.9	0.82

Fig.9 Reaction performance of Pickering emulsions with different catalyst concentrations during batch reactions

Fig.10 Reaction performance of reinforced Pickering emulsions with different crosslinker amounts during batch reactions

Fig.11 The reaction performance of reinforced Pickering emulsion in a fix bed reactor

Table 2 Comparison of the operating conditions and results in this work with literatures

文献	催化剂	FA∶PA（摩尔比）	温度/℃	压力/MPa	收率/%	反应过程	催化剂分离
[28]	二乙胺+乙酸水溶液	1.05∶1	132	5.0	99	连续	是
[29]	二乙胺乙酸盐	1∶1	40	常压	97	间歇	是
[30]	层状双氢氧化物	1∶1	60	常压	30	间歇	否
[12]	羟脯氨酸	1∶1	43	常压	45	间歇	否
[15]	仲胺接枝D301树脂	2∶1	80	常压	40	连续	否
本工作	L-脯氨酸	1.1∶1	45	常压	45	连续	否

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