Pickering乳液催化非均相羟醛缩合反应研究

doi:10.11949/0438-1157.20221196

化工学报 ›› 2023, Vol. 74 ›› Issue (1): 449-458.DOI: 10.11949/0438-1157.20221196

• 催化、动力学与反应器 • 上一篇下一篇

Pickering乳液催化非均相羟醛缩合反应研究

陈余¹^,²(), 郑晓妍¹^,³, 赵辉¹, 王二强², 李杰¹^,⁴(), 李春山¹^,²()

^1.中国科学院过程工程研究所，离子液体清洁过程北京市重点实验室，北京 100190
^2.中国科学院大学化工学院，北京 101408
^3.北京石油化工学院新材料与化工学院，北京 102617
^4.先进能源科学与技术广东省实验室，广东惠州 516003

收稿日期:2022-09-01 修回日期:2022-10-27 出版日期:2023-01-05 发布日期:2023-03-20
通讯作者: 李杰,李春山
作者简介:陈余（1997—），女，博士研究生，yuchen@ipe.ac.cn
基金资助:
国家杰出青年自然科学基金项目(22025803);国家自然科学基金青年科学基金项目(22108278);河北省自然科学基金项目(B2021103012)

Heterogeneous aldol condensation catalyzed with Pickering emulsion

Yu CHEN¹^,²(), Xiaoyan ZHENG¹^,³, Hui ZHAO¹, Erqiang WANG², Jie LI¹^,⁴(), Chunshan LI¹^,²()

^1.Beijing Key Laboratory of Ionic Liquids Clean Process, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China
^2.School of Chemical Engineering, University of Chinese Academy of Sciences, Beijing 101408, China
^3.College of New Materials and Chemical Engineering, Beijing Institute of Petrochemical Technology, Beijing 102617, China
^4.Advanced Energy Science and Technology Guangdong Laboratory, Huizhou 516003, Guangdong, China

Received:2022-09-01 Revised:2022-10-27 Online:2023-01-05 Published:2023-03-20
Contact: Jie LI, Chunshan LI

摘要/Abstract

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

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

中图分类号:

TQ 032.4

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.

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.

图/表 13

图1 煤基乙烯/合成气法生产MMA反应路线

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

图2 Pickering乳液制备和固定床连续催化反应过程

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

图3 不同MTMS用量改性SiO2颗粒的接触角及其稳定的Pickering乳液显微镜图

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

图4 不同MTMS用量改性SiO2颗粒的FT-IR谱图

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

图5 不同乳化剂用量下的液滴直径及加热前后Pickering乳液显微镜图

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

图6 不同交联剂及交联方式制备的强化Pickering乳液显微镜图像

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

图7 多孔微球SEM图像

Fig.7 SEM images of porous microspheres

图8 多孔微球的N2吸附-脱附等温线和孔径分布

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

表1 不同交联剂用量合成多孔微球孔结构表征

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

图9 间歇反应过程中不同催化剂浓度下Pickering乳液的反应性能

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

图10 间歇反应过程中不同交联剂用量下强化Pickering乳液的反应性能

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

图11 强化Pickering乳液催化体系反应性能

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

表2 本工作中的操作条件和结果与文献的比较

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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Pickering乳液催化非均相羟醛缩合反应研究

Heterogeneous aldol condensation catalyzed with Pickering emulsion

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