Controlled methylamine synthesis in a membrane reactor featuring a highly steam selective K+-LTA membrane

Research output: Contribution to journal › Article › Research › peer review

Authors

  • Felix Rieck genannt Best
  • Alexander Mundstock
  • Hannes Richter
  • Patrick A. Kißling
  • Karen D.J. Hindricks
  • Aisheng Huang
  • Peter Behrens
  • Jürgen Caro

Research Organisations

External Research Organisations

  • Fraunhofer Institute for Ceramic Technologies and Systems (IKTS)
  • East China Normal University
  • South China University of Technology
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Details

Original languageEnglish
Article number111920
JournalMicroporous and Mesoporous Materials
Volume337
Early online date16 Apr 2022
Publication statusPublished - May 2022

Abstract

Water permeation through a hydrophilic zeolite membrane can be used to promote reactions under equilibrium controlled conditions through the in situ removal of the by-product water. In the methylamine synthesis, mono- (MMA), di- (DMA) and trimethylamine (TMA) are formed by the successive methylation of ammonia with methanol (MeOH) over a mildly acidic catalyst. The methylamine yield can be increased through selective water extraction from the reactor through a membrane. Since both reactants and water have similar molecular kinetic diameters below 3.7 Å, because of the limited steam selectivity of the commonly used hydrophilic Na-LTA membrane (zeolite 4A), not only water has been removed. Therefore, in this work a K-LTA membrane, which was obtained by ion exchange with a reduced pore window diameter of 3 Å and thus with a higher water selectivity, was used in the membrane-supported methylamine synthesis. When replacing the Na-LTA with the K-LTA membrane, the H2O/MeOH mixed gas separation factor increases up to 1100 and the H2O/NH3 separation could also be improved. This in turn leads to an overall boost of the higher methylated amines DMA and TMA in methylamine synthesis. When using the narrow-pore aluminosilicate catalyst H-SSZ-13 with CHA structure, the application of the K-LTA membrane increases the share of the industrially desired product DMA from 51% without membrane to 74% with slightly increased conversion. When using the large-pore catalyst H-MOR, the thermodynamically most stable product TMA can be formed and the selectivity was increased from 35% without membrane to 41% with the K-LTA membrane.

Keywords

    Cation exchange, Hydrophilic LTA membrane, In situ water removal, Membrane reactor, Methylamines, Zeolite membranes

ASJC Scopus subject areas

Cite this

Controlled methylamine synthesis in a membrane reactor featuring a highly steam selective K+-LTA membrane. / Rieck genannt Best, Felix; Mundstock, Alexander; Richter, Hannes et al.
In: Microporous and Mesoporous Materials, Vol. 337, 111920, 05.2022.

Research output: Contribution to journal › Article › Research › peer review

Rieck genannt Best, F, Mundstock, A, Richter, H, Kißling, PA, Hindricks, KDJ, Huang, A, Behrens, P & Caro, J 2022, 'Controlled methylamine synthesis in a membrane reactor featuring a highly steam selective K+-LTA membrane', Microporous and Mesoporous Materials, vol. 337, 111920. https://doi.org/10.1016/j.micromeso.2022.111920
Rieck genannt Best, F., Mundstock, A., Richter, H., Kißling, P. A., Hindricks, K. D. J., Huang, A., Behrens, P., & Caro, J. (2022). Controlled methylamine synthesis in a membrane reactor featuring a highly steam selective K+-LTA membrane. Microporous and Mesoporous Materials, 337, Article 111920. https://doi.org/10.1016/j.micromeso.2022.111920
Rieck genannt Best F, Mundstock A, Richter H, Kißling PA, Hindricks KDJ, Huang A et al. Controlled methylamine synthesis in a membrane reactor featuring a highly steam selective K+-LTA membrane. Microporous and Mesoporous Materials. 2022 May;337:111920. Epub 2022 Apr 16. doi: 10.1016/j.micromeso.2022.111920
Rieck genannt Best, Felix ; Mundstock, Alexander ; Richter, Hannes et al. / Controlled methylamine synthesis in a membrane reactor featuring a highly steam selective K+-LTA membrane. In: Microporous and Mesoporous Materials. 2022 ; Vol. 337.
Download
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title = "Controlled methylamine synthesis in a membrane reactor featuring a highly steam selective K+-LTA membrane",
abstract = "Water permeation through a hydrophilic zeolite membrane can be used to promote reactions under equilibrium controlled conditions through the in situ removal of the by-product water. In the methylamine synthesis, mono- (MMA), di- (DMA) and trimethylamine (TMA) are formed by the successive methylation of ammonia with methanol (MeOH) over a mildly acidic catalyst. The methylamine yield can be increased through selective water extraction from the reactor through a membrane. Since both reactants and water have similar molecular kinetic diameters below 3.7 {\AA}, because of the limited steam selectivity of the commonly used hydrophilic Na-LTA membrane (zeolite 4A), not only water has been removed. Therefore, in this work a K-LTA membrane, which was obtained by ion exchange with a reduced pore window diameter of 3 {\AA} and thus with a higher water selectivity, was used in the membrane-supported methylamine synthesis. When replacing the Na-LTA with the K-LTA membrane, the H2O/MeOH mixed gas separation factor increases up to 1100 and the H2O/NH3 separation could also be improved. This in turn leads to an overall boost of the higher methylated amines DMA and TMA in methylamine synthesis. When using the narrow-pore aluminosilicate catalyst H-SSZ-13 with CHA structure, the application of the K-LTA membrane increases the share of the industrially desired product DMA from 51% without membrane to 74% with slightly increased conversion. When using the large-pore catalyst H-MOR, the thermodynamically most stable product TMA can be formed and the selectivity was increased from 35% without membrane to 41% with the K-LTA membrane.",
keywords = "Cation exchange, Hydrophilic LTA membrane, In situ water removal, Membrane reactor, Methylamines, Zeolite membranes",
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note = "Funding Information: The Deutsche Forschungsgemeinschaft ( DFG, German Research Foundation ) is thanked for financing the project ( CA147/21-1 ). Patrick A. Kiβling thanks the DFG (Project BI1708/5-1 ) [ 35 ]. Additionally, the project has in parts been funded by the DFG under Germany's Excellence Strategy within the Cluster of Excellence PhoenixD (EXC 2122, Project ID 390833453 ). Karen Hindricks is thankful for a grant from the Deutsche Studienstiftung.",
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Download

TY - JOUR

T1 - Controlled methylamine synthesis in a membrane reactor featuring a highly steam selective K+-LTA membrane

AU - Rieck genannt Best, Felix

AU - Mundstock, Alexander

AU - Richter, Hannes

AU - Kißling, Patrick A.

AU - Hindricks, Karen D.J.

AU - Huang, Aisheng

AU - Behrens, Peter

AU - Caro, Jürgen

N1 - Funding Information: The Deutsche Forschungsgemeinschaft ( DFG, German Research Foundation ) is thanked for financing the project ( CA147/21-1 ). Patrick A. Kiβling thanks the DFG (Project BI1708/5-1 ) [ 35 ]. Additionally, the project has in parts been funded by the DFG under Germany's Excellence Strategy within the Cluster of Excellence PhoenixD (EXC 2122, Project ID 390833453 ). Karen Hindricks is thankful for a grant from the Deutsche Studienstiftung.

PY - 2022/5

Y1 - 2022/5

N2 - Water permeation through a hydrophilic zeolite membrane can be used to promote reactions under equilibrium controlled conditions through the in situ removal of the by-product water. In the methylamine synthesis, mono- (MMA), di- (DMA) and trimethylamine (TMA) are formed by the successive methylation of ammonia with methanol (MeOH) over a mildly acidic catalyst. The methylamine yield can be increased through selective water extraction from the reactor through a membrane. Since both reactants and water have similar molecular kinetic diameters below 3.7 Å, because of the limited steam selectivity of the commonly used hydrophilic Na-LTA membrane (zeolite 4A), not only water has been removed. Therefore, in this work a K-LTA membrane, which was obtained by ion exchange with a reduced pore window diameter of 3 Å and thus with a higher water selectivity, was used in the membrane-supported methylamine synthesis. When replacing the Na-LTA with the K-LTA membrane, the H2O/MeOH mixed gas separation factor increases up to 1100 and the H2O/NH3 separation could also be improved. This in turn leads to an overall boost of the higher methylated amines DMA and TMA in methylamine synthesis. When using the narrow-pore aluminosilicate catalyst H-SSZ-13 with CHA structure, the application of the K-LTA membrane increases the share of the industrially desired product DMA from 51% without membrane to 74% with slightly increased conversion. When using the large-pore catalyst H-MOR, the thermodynamically most stable product TMA can be formed and the selectivity was increased from 35% without membrane to 41% with the K-LTA membrane.

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KW - Cation exchange

KW - Hydrophilic LTA membrane

KW - In situ water removal

KW - Membrane reactor

KW - Methylamines

KW - Zeolite membranes

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DO - 10.1016/j.micromeso.2022.111920

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VL - 337

JO - Microporous and Mesoporous Materials

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