Reaction networks and thermodynamic analysis of methacrolein synthesis catalyzed by sec-amine ionic liquids

ZHENG Xiaoyan; LI Jianhui; LI Jie; WANG Gang; LI Zengxi; WANG Erqiang; LI Chunshan

doi:10.11949/0438-1157.20260412

您当前的位置：

首页 >

文章列表页 >

Reaction networks and thermodynamic analysis of methacrolein synthesis catalyzed by sec-amine ionic liquids

更新时间：2026-05-25

- Reaction networks and thermodynamic analysis of methacrolein synthesis catalyzed by sec-amine ionic liquids
- CIESC Journal (2026)
- 作者机构：
  
  1.中国科学院成都有机化学研究所，四川成都 610041
  2.中国石油大学（北京）化学工程与环境学院，重质油全国重点实验室，北京 102249
  3.中国科学院过程工程研究所，北京市固体锂电池与储能过程重点实验室，介科学与工程全国重点实验室，北京 100190
  4.中国科学院大学化工学院，北京 101408
- 作者简介：
- 基金信息：
- DOI：10.11949/0438-1157.20260412
  CLC： O 643.32
- Received：27 March 2026，
  
  Revised：2026-05-19，
  
  Accepted：20 May 2026，
- 稿件说明：
移动端阅览
ZHENG Xiaoyan, LI Jianhui, LI Jie, et al. Reaction networks and thermodynamic analysis of methacrolein synthesis catalyzed by sec-amine ionic liquids[J/OL]. CIESC Journal, 2026.
DOI：

ZHENG Xiaoyan, LI Jianhui, LI Jie, et al. Reaction networks and thermodynamic analysis of methacrolein synthesis catalyzed by sec-amine ionic liquids[J/OL]. CIESC Journal, 2026. DOI： 10.11949/0438-1157.20260412.

摘要

近年来，仲胺离子液体催化甲醛与丙醛经Mannich缩合反应制备甲基丙烯醛（MAL）受到广泛关注。针对该均相反应体系，筛选出

-乙基环己胺丁酸盐离子液体为最优催化剂。采用气相色谱-质谱联用技术（GC-MS）对反应体系中的主及副产物进行结构鉴定，构建了由目标反应及主要副反应组成的反应网络。利用基团贡献法估算了相关物质的基础热力学参数，并对不同方法得到的结果进行了对比分析，进而计算了各反应的吉布斯自由能变与平衡常数。本工作为仲胺离子液体催化甲醛-丙醛缩合制备MAL反应路径研究和催化体系优化提供了理论依据。

Abstract

In recent years

the synthesis of methacrolein (MAL) from formaldehyde and propionaldehyde

via

Mannich reaction catalyzed by sec-amine ionic liquids has attracted considerable attention. In this homogeneous reaction system

-ethylcyclohexylamine butyrate ionic liquid was identified as th

e optimal catalyst. The main products and byproducts were structurally identified by gas chromatography-mass spectrometry (GC-MS)

and a reaction network composed of the target reaction and the main side reactions was constructed. The basic thermodynamic properties of the relevant substances were estimated using group contribution methods

and the results obtained from different methods were comparatively analyzed. On this basis

the Gibbs free energy changes and equilibrium constants of the individual reactions were calculated. This work provides a theoretical basis for elucidating the reaction pathways and optimizing the catalytic system for MAL synthesis from formaldehyde and propionaldehyde over sec-amine ionic liquids.

关键词

Keywords

references

Deshpande R M , Diwakar M M , Mahajan A N , et al . Biphasic catalysis for a selective oxo–Mannich tandem synthesis of methacrolein [J ] . Journal of Molecular Catalysis A: Chemical , 2004 , 211 ( 1/2 ): 49 - 53 .

Zhao H , Ran R , Wang L , et al . Novel continuous process for methacrolein production in numerous droplet reactors [J ] . AIChE Journal , 2020 , 66 ( 7 ): e16239 .

Zhang T H , Bian Y H , Wang L M , et al . Continuous synthesis of methacrolein over sulfonic acid resin catalysts: unraveling the effect of acid strength and solvent permittivity [J ] . Industrial & Engineering Chemistry Research , 2023 , 62 ( 33 ): 12949 - 12962 .

Guo X J , Huang C P , Chen B H . One-step synthesis of methylmethacrylate from methacrolein over Keggin-type heteropoly compounds [J ] . Korean Journal of Chemical Engineering , 2008 , 25 ( 4 ): 675 - 680 .

Moens L , Ruiz P , Delmon B , et al . A simplified partial ionic charge model to evaluate the role played by bismuth pyrostannate in multiphase catalysts for the selective oxidation of isobutene to methacrolein [J ] . Applied Catalysis A: General , 2003 , 249 ( 2 ): 365 - 374 .

Li Q H , Zhao H H , Yang J , et al . Insight into the selective oxidation of isobutene to methacrolein over Ce-accelerated Mo-Bi-Fe-Co-K-O catalyst [J ] . Molecular Catalysis , 2022 , 527 : 112401 .

Guan J Q , Wu S J , Wang H S , et al . Synthesis and characterization of MoVTeCeO catalysts and their catalytic performance for selective oxidation of isobutane and isobutylene [J ] . Journal of Catalysis , 2007 , 251 ( 2 ): 354 - 362 .

Zhai Z , Wang X , Licht R , et al . Selective oxidation and oxidative dehydrogenation of hydrocarbons on bismuth vanadium molybdenum oxide [J ] . Journal of Catalysis , 2015 , 325 : 87 - 100 .

Liu H C , Gaigneaux E M , Imoto H , et al . Novel Re–Sb–O catalysts for the selective oxidation of isobutane and isobutylene [J ] . Applied Catalysis A: General , 2000 , 202 ( 2 ): 251 - 264 .

王国强 . 碳四烃综合利用研究 [J ] . 中国石油和化工标准与质量 , 2014 , 34 ( 10 ): 16 - 17 .

Wang G Q . Study on comprehensive utilization of C4 hydrocarbons [J ] . China Petroleum and Chemical Standard and Quality , 2014 , 34 ( 10 ): 16 - 17 .

Sánchez-Velandia J E , Villa A L . Selective synthesis of high-added value chemicals from α-pinene epoxide and limonene epoxide isomerization over mesostructured catalysts: Effect of the metal loading and solvent [J ] . Catalysis Today , 2022 , 394 : 208 - 218 .

Yan H W , Huo F , Li P , et al . Mild catalytic mechanism of the Mannich reaction for synthesizing methylacrolein by sec-amine short-chain aliphatic acid ionic liquid catalysts [J ] . ACS Sustainable Chemistry & Engineering , 2022 , 10 ( 20 ): 6687 - 6698 .

Zhao H , Li J , Wang L , et al . Pickering emulsion stabilized by dual stabilizer: A novel reaction/separation system for methacrolein synthesis [J ] . Chemical Engineering Science , 2021 , 229 : 116038 .

Wang X , Li C , Wang M T , et al . The preparation of methacrolein by Mannich reaction using a bifunctional heterogeneous catalyst [J ] . Molecular Catalysis , 2025 , 584 : 115307 .

常富荣 , 母灿先 , 李翔 . 二乙醇胺/磷酸催化甲醛和丙醛缩合制备2-甲基丙烯醛 [J ] . 工业催化 , 2011 , 19 ( 8 ): 62 - 64 .

Chang F R , Mu C X , Li X . Synthesis of 2-methyl propenal via the condensation of methanal and propanal catalyzed by diethanolamine/H 3 PO 4 [J ] . Industrial Catalysis , 2011 , 19 ( 8 ): 62 - 64 .

Yu J Y , Jensen A D , Wang L , et al . Catalytic synthesis of methacrolein via the condensation of formaldehyde and propionaldehyde with L-proline [J ] . Green Chemistry , 2020 , 22 ( 13 ): 4222 - 4230 .

李玉超 , 闫瑞一 , 王蕾 , 等 . 甲醛和丙醛缩合制备甲基丙烯醛反应动力学 [J ] . 过程工程学报 , 2012 , 12 ( 4 ): 602 - 607 .

Li Y C , Yan R Y , Wang L , et al . Reaction kinetics for preparation of methacrolein by condensation of formaldehyde with propionaldehyde [J ] . The Chinese Journal of Process Engineering , 2012 , 12 ( 4 ): 602 - 607 .

Li Y C , Yan R Y , Wang L , et al . Synthesis of methacrolein by condensation of propionaldehyde with formaldehyde [J ] . Advanced Materials Research , 2011 , 396/ 397 / 398 : 1094 - 1097 .

Wang T , Li J , Yan H W , et al . Mechanism and kinetic study on synthesis of methacrolein catalyzed by amine/acid [J ] . Catalysts , 2023 , 13 ( 5 ): 799 .

Zhao Q , Zhao H , Wang G , et al . Kinetic and mechanistic insights into the roles of protonated morpholine species and weak acidic environment in methylacrolein production catalyzed by morpholine/acid [J ] . Chemical Engineering Journal , 2023 , 460 : 140409 .

雷亮 . 甲醛丙醛缩合制备甲基丙烯醛反应过程研究及工艺开发 [D ] . 天津：天津大学 , 2017 .

Lei L . Experimental research and process development for the synthesis of methacrolein by condensation of propanal with formaldehyde [D ] . Tianjin : Tianjin University , 2017 .

闫瀚文 . 离子液体催化甲基丙烯醛温和制备机制研究 [D ] . 银川：宁夏大学 , 2022 .

Yan H W . Mild catalytic mechanism of synthesizing methylacrolein by ionic liquids catalysts [D ] . Yinchuan : Ningxia University , 2022 .

Fan L , Xu B H , Li J , et al . Kinetic studies on both synthesis of methacrolein catalyzed by an ionic liquid and catalyst deactivation [J ] . Industrial & Engineering Chemistry Research , 2021 , 60 ( 15 ): 5411 - 5420 .

Yan R Y , Lv Z P , Tang H G , et al . Mechanistic insight into methacrolein formation from formaldehyde and propionaldehyde [J ] . Catalysis Letters , 2022 , 152 ( 3 ): 799 - 805 .

陈余 , 郑晓妍 , 赵辉 , 等 . 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 .

Chen Y , Zheng X Y , Zhao H , et al . Heterogeneous aldol condensation catalyzed with Pickering emulsion [J ] . CIESC Journal , 2023 , 74 ( 1 ): 449 - 458 .

汪韬 . 甲醛与丙醛合成甲基丙烯醛的胺/酸催化剂研究 [D ] . 沈阳：沈阳化工大学 , 2023 .

Wang T . Study on amine/acid catalysts for synthesis of methacrolein from formaldehyde and propionaldehyde [D ] . Shenyang : Shenyang University of Chemical Technology , 2023 .

樊柳 . 甲基丙烯醛合成过程离子液体催化剂失活机理及动力学研究 [D ] . 北京：中国科学院大学(中国科学院过程工程研究所) , 2021 .

Fan L . Deactivation mechanism and kinetic studies of ionic liquid catalysts for methacrolein synthesis [D ] . Beijing : Institute of Process Engineering, Chinese Academy of Sciences , 2021 .

蓝佳龙 . 甲基丁炔醇选择性加氢反应的研究 [D ] . 杭州：浙江大学 , 2018 .

Lan J L . Study on the selective hydrogenation of 2-methyl-3-butene-2-ol [D ] . Hangzhou : Zhejiang University , 2018 .

朱嘉嘉 . 甲醇制丙烯动力学研究及反应器模拟 [D ] . 杭州：浙江大学 , 2017 .

Zhu J J . Kinetics of methanol to propene and reactor simulation [D ] . Hangzhou : Zhejiang University , 2017 .

Sumiya Y , Tabata Y , Maeda S . Understanding the acetalization reaction based on its reaction path network [J ] . ChemSystemsChem , 2020 , 2 : e1900022 .

Davey S G . A reaction regulation network [J ] . Nature Reviews Chemistry , 2019 , 3 ( 11 ): 623 .

Ji W Q , Deng S L . Autonomous discovery of unknown reaction pathways from data by chemical reaction neural network [J ] . The Journal of Physical Chemistry A , 2021 , 125 ( 4 ): 1082 - 1092 .

伍艳辉 , 梁泽磊 , 刘剑 , 等 . 乙醛缩合反应体系热力学计算和分析 [J ] . 同济大学学报(自然科学版) , 2011 , 39 ( 3 ): 456 - 461 .

Wu Y H , Liang Z L , Liu J , et al . Thermodynamics of aldol condensation of acetaldehyde [J ] . Journal of Tongji University (Natural Science) , 2011 , 39 ( 3 ): 456 - 461 .

许玥 . 离子液体催化合成季戊四醇的研究 [D ] . 贵阳：贵州大学 , 2022 .

Xu Y . Study on the synthesis of pentaerythritol catalyzed by ionic liquids [D ] . Guiyang : Guizhou University , 2022 .

伍艳辉 , 任伟丽 , 吴高胜 , 等 . 甲醛和异丁醛羟醛缩合反应体系热力学分析 [J ] . 同济大学学报(自然科学版) , 2017 , 45 ( 10 ): 1549 - 1554 .

Wu Y H , Ren W L , Wu G S , et al . Thermodynamic analysis of aldol condendation of formaldehyde and isobutyraldehyde [J ] . Journal of Tongji University (Natural Science) , 2017 , 45 ( 10 ): 1549 - 1554 .

洪鹏 . 3-甲基-3-戊烯-2-酮合成过程的研究 [D ] . 福州：福州大学 , 2020 .

Hong P . Study on 3-methyl-3-penten-2-one synthesis [D ] . Fuzhou : Fuzhou University , 2020 .

Views

下载量

CSCD

Alert me when the article has been cited

提交

Tools

Publicity Resources

Perfromance assessment of auto-cascade cycle integrating fractionation and flash separation

One-step extraction and separation of high purity chitin based on choline ionic liquid

Extraction of bicyclic S/N-compounds from FCC diesel with ionic liquid: experimental and molecular insight

Hypergolic ignition characteristics and propulsion performance of imidazolium dicyanamide ionic liquids blended with furfuryl alcohol

Recent progress on application of COSMO-RS model in screening of ionic liquids/deep eutectic solvents

Related Author

LI Yinlong

LIU Guoqiang

YAN Gang

FENG Mi

ZHANG Jie

LYU Xingmei

JIANG Siqi

HU Yufeng

Related Institution

School of Energy and Power Engineering, Xi’an Jiaotong University

Institute of Process Engineering, Chinese Academy of Sciences

Longzihu New Energy Laboratory, Zhengzhou Institute of Emerging Industrial Technology

Beijing BW Techtextile Company Limited by Shares

Hubei Key Laboratory of Biomass Fibers and Eco-dyeing & Finishing, College of Chemistry and Chemical Engineering, Wuhan Textile University

⁰