Multifunctional Amine Modifiers for Selective Dehydration of Methyl Lactate to Acrylates

Yutong Pang; Choong Sze Lee; Bess Vlaisavljevich; Christopher P. Nicholas; Paul J. Dauenhauer

doi:10.1021/jacsau.2c00513

Multifunctional Amine Modifiers for Selective Dehydration of Methyl Lactate to Acrylates

Yutong Pang, Choong Sze Lee, Bess Vlaisavljevich, Christopher P. Nicholas, Paul J. Dauenhauer

Chemical Engineering and Materials Science

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

4 Scopus citations

Abstract

Dehydration of methyl lactate to acrylic acid and methyl acrylate was experimentally evaluated over a Na-FAU zeolite catalyst impregnated with multifunctional diamines. 1,2-Bis(4-pyridyl)ethane (12BPE) and 4,4′-trimethylenedipyridine (44TMDP), at a nominal loading of 40 wt % or two molecules per Na-FAU supercage, afforded a dehydration selectivity of 96 ± 3% over 2000 min time on stream. Although 12BPE and 44TMDP have van der Waals diameters approximately 90% of the Na-FAU window opening diameter, both flexible diamines interact with internal active sites of Na-FAU as characterized by infrared spectroscopy. During continuous reaction at 300 °C, the amine loadings in Na-FAU remained constant for 12BPE but decreased as much as 83% for 44TMDP. Tuning the weighted hourly space velocity (WHSV) from 0.9 to 0.2 h^-1 afforded a yield as high as 92% at a selectivity of 96% with 44TMDP impregnated Na-FAU, resulting in the highest yield reported to date.

Original language	English (US)
Pages (from-to)	368-377
Number of pages	10
Journal	JACS Au
Volume	3
Issue number	2
DOIs	https://doi.org/10.1021/jacsau.2c00513
State	Published - Feb 27 2023

Bibliographical note

Funding Information:
We acknowledge financial support of the NSF Center for Sustainable Polymers, an NSF Center for Chemical Innovation at the University of Minnesota (CHE-1901635). The authors acknowledge the Minnesota Supercomputing Institute (MSI, http://www.msi.umn.edu/) at the University of Minnesota for providing resources that contributed to the research results reported within this paper.

Funding Information:
We acknowledge financial support of the NSF Center for Sustainable Polymers, an NSF Center for Chemical Innovation at the University of Minnesota (CHE-1901635). The authors acknowledge the Minnesota Supercomputing Institute (MSI, http://www.msi.umn.edu/ ) at the University of Minnesota for providing resources that contributed to the research results reported within this paper.

Publisher Copyright:
© 2023 The Authors. Published by American Chemical Society.

Keywords

Acrylic Acid
Amine
Dehydration
Lactic Acid
Zeolite

PubMed: MeSH publication types

Journal Article

Access

10.1021/jacsau.2c00513

OpenUrl availability

Full text

Cite this

@article{3cdca8600e544cccaade2f4aaad1d03b,

title = "Multifunctional Amine Modifiers for Selective Dehydration of Methyl Lactate to Acrylates",

abstract = "Dehydration of methyl lactate to acrylic acid and methyl acrylate was experimentally evaluated over a Na-FAU zeolite catalyst impregnated with multifunctional diamines. 1,2-Bis(4-pyridyl)ethane (12BPE) and 4,4′-trimethylenedipyridine (44TMDP), at a nominal loading of 40 wt % or two molecules per Na-FAU supercage, afforded a dehydration selectivity of 96 ± 3% over 2000 min time on stream. Although 12BPE and 44TMDP have van der Waals diameters approximately 90% of the Na-FAU window opening diameter, both flexible diamines interact with internal active sites of Na-FAU as characterized by infrared spectroscopy. During continuous reaction at 300 °C, the amine loadings in Na-FAU remained constant for 12BPE but decreased as much as 83% for 44TMDP. Tuning the weighted hourly space velocity (WHSV) from 0.9 to 0.2 h-1 afforded a yield as high as 92% at a selectivity of 96% with 44TMDP impregnated Na-FAU, resulting in the highest yield reported to date.",

keywords = "Acrylic Acid, Amine, Dehydration, Lactic Acid, Zeolite",

author = "Yutong Pang and Lee, {Choong Sze} and Bess Vlaisavljevich and Nicholas, {Christopher P.} and Dauenhauer, {Paul J.}",

note = "Funding Information: We acknowledge financial support of the NSF Center for Sustainable Polymers, an NSF Center for Chemical Innovation at the University of Minnesota (CHE-1901635). The authors acknowledge the Minnesota Supercomputing Institute (MSI, http://www.msi.umn.edu/) at the University of Minnesota for providing resources that contributed to the research results reported within this paper. Funding Information: We acknowledge financial support of the NSF Center for Sustainable Polymers, an NSF Center for Chemical Innovation at the University of Minnesota (CHE-1901635). The authors acknowledge the Minnesota Supercomputing Institute (MSI, http://www.msi.umn.edu/ ) at the University of Minnesota for providing resources that contributed to the research results reported within this paper. Publisher Copyright: {\textcopyright} 2023 The Authors. Published by American Chemical Society.",

year = "2023",

month = feb,

day = "27",

doi = "10.1021/jacsau.2c00513",

language = "English (US)",

volume = "3",

pages = "368--377",

journal = "JACS Au",

issn = "2691-3704",

publisher = "American Chemical Society",

number = "2",

}

TY - JOUR

T1 - Multifunctional Amine Modifiers for Selective Dehydration of Methyl Lactate to Acrylates

AU - Pang, Yutong

AU - Lee, Choong Sze

AU - Vlaisavljevich, Bess

AU - Nicholas, Christopher P.

AU - Dauenhauer, Paul J.

N1 - Funding Information: We acknowledge financial support of the NSF Center for Sustainable Polymers, an NSF Center for Chemical Innovation at the University of Minnesota (CHE-1901635). The authors acknowledge the Minnesota Supercomputing Institute (MSI, http://www.msi.umn.edu/) at the University of Minnesota for providing resources that contributed to the research results reported within this paper. Funding Information: We acknowledge financial support of the NSF Center for Sustainable Polymers, an NSF Center for Chemical Innovation at the University of Minnesota (CHE-1901635). The authors acknowledge the Minnesota Supercomputing Institute (MSI, http://www.msi.umn.edu/ ) at the University of Minnesota for providing resources that contributed to the research results reported within this paper. Publisher Copyright: © 2023 The Authors. Published by American Chemical Society.

PY - 2023/2/27

Y1 - 2023/2/27

N2 - Dehydration of methyl lactate to acrylic acid and methyl acrylate was experimentally evaluated over a Na-FAU zeolite catalyst impregnated with multifunctional diamines. 1,2-Bis(4-pyridyl)ethane (12BPE) and 4,4′-trimethylenedipyridine (44TMDP), at a nominal loading of 40 wt % or two molecules per Na-FAU supercage, afforded a dehydration selectivity of 96 ± 3% over 2000 min time on stream. Although 12BPE and 44TMDP have van der Waals diameters approximately 90% of the Na-FAU window opening diameter, both flexible diamines interact with internal active sites of Na-FAU as characterized by infrared spectroscopy. During continuous reaction at 300 °C, the amine loadings in Na-FAU remained constant for 12BPE but decreased as much as 83% for 44TMDP. Tuning the weighted hourly space velocity (WHSV) from 0.9 to 0.2 h-1 afforded a yield as high as 92% at a selectivity of 96% with 44TMDP impregnated Na-FAU, resulting in the highest yield reported to date.

AB - Dehydration of methyl lactate to acrylic acid and methyl acrylate was experimentally evaluated over a Na-FAU zeolite catalyst impregnated with multifunctional diamines. 1,2-Bis(4-pyridyl)ethane (12BPE) and 4,4′-trimethylenedipyridine (44TMDP), at a nominal loading of 40 wt % or two molecules per Na-FAU supercage, afforded a dehydration selectivity of 96 ± 3% over 2000 min time on stream. Although 12BPE and 44TMDP have van der Waals diameters approximately 90% of the Na-FAU window opening diameter, both flexible diamines interact with internal active sites of Na-FAU as characterized by infrared spectroscopy. During continuous reaction at 300 °C, the amine loadings in Na-FAU remained constant for 12BPE but decreased as much as 83% for 44TMDP. Tuning the weighted hourly space velocity (WHSV) from 0.9 to 0.2 h-1 afforded a yield as high as 92% at a selectivity of 96% with 44TMDP impregnated Na-FAU, resulting in the highest yield reported to date.

KW - Acrylic Acid

KW - Amine

KW - Dehydration

KW - Lactic Acid

KW - Zeolite

UR - http://www.scopus.com/inward/record.url?scp=85146167103&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85146167103&partnerID=8YFLogxK

U2 - 10.1021/jacsau.2c00513

DO - 10.1021/jacsau.2c00513

M3 - Article

C2 - 36873694

AN - SCOPUS:85146167103

SN - 2691-3704

VL - 3

SP - 368

EP - 377

JO - JACS Au

JF - JACS Au

IS - 2

ER -

Multifunctional Amine Modifiers for Selective Dehydration of Methyl Lactate to Acrylates

Abstract

Bibliographical note

Keywords

PubMed: MeSH publication types

Access

OpenUrl availability

Other files and links

Fingerprint

Cite this