Kinetic Analysis of Hexose Conversion to Methyl Lactate by Sn Beta: Effects of Substrate Masking and of Water

Irene Tosi, Anders Riisager, Esben Taarning, Pernille Rose Jensen, Sebastian Meier*

*Corresponding author for this work

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Abstract

Simple sugars bear promise as substrates for the formation of fuels and chemicals using heterogeneous catalysts in alcoholic solvents. Sn-Beta is a particularly well suited catalyst for the cleavage, isomerization and dehydration of sugars into more valuable chemicals. In order to understand these processes and save resources and time by optimising them, kinetic and mechanistic analyses are helpful. Herein, we study substrate entry into the Sn-Beta catalysed methyl lactate process using abundant hexose substrates. NMR spectroscopy is applied to show that the formation of methyl lactate occurs in two kinetic regimes for fructose, glucose and sucrose. The majority of methyl lactate is not formed from the substrate directly, but from methyl fructosides in a slow regime. At 160 °C, more than 40% of substrate carbon are masked
(i.e. reversibly protected in situ) as methyl fructosides within few minutes when using hydrothermally synthesised Sn-Beta, while more than 60% methyl fructosides can be produced within few minutes using post synthetically synthesised Sn-Beta. A significant fraction of substrate thus is masked by rapid methyl fructoside formation prior to subsequent slow release of fructose. This release is the rate limiting step in the Sn-Beta catalysed methyl lactate process, but can be accelerated by the addition of small amounts of water at the expense of maximum methyl lactate yield.
Original languageEnglish
JournalCatalysis Science & Technology
Volume18
Issue number8
Pages (from-to)2137-2145
Number of pages9
ISSN2044-4753
DOIs
Publication statusPublished - 2018

Cite this

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title = "Kinetic Analysis of Hexose Conversion to Methyl Lactate by Sn Beta: Effects of Substrate Masking and of Water",
abstract = "Simple sugars bear promise as substrates for the formation of fuels and chemicals using heterogeneous catalysts in alcoholic solvents. Sn-Beta is a particularly well suited catalyst for the cleavage, isomerization and dehydration of sugars into more valuable chemicals. In order to understand these processes and save resources and time by optimising them, kinetic and mechanistic analyses are helpful. Herein, we study substrate entry into the Sn-Beta catalysed methyl lactate process using abundant hexose substrates. NMR spectroscopy is applied to show that the formation of methyl lactate occurs in two kinetic regimes for fructose, glucose and sucrose. The majority of methyl lactate is not formed from the substrate directly, but from methyl fructosides in a slow regime. At 160 °C, more than 40{\%} of substrate carbon are masked(i.e. reversibly protected in situ) as methyl fructosides within few minutes when using hydrothermally synthesised Sn-Beta, while more than 60{\%} methyl fructosides can be produced within few minutes using post synthetically synthesised Sn-Beta. A significant fraction of substrate thus is masked by rapid methyl fructoside formation prior to subsequent slow release of fructose. This release is the rate limiting step in the Sn-Beta catalysed methyl lactate process, but can be accelerated by the addition of small amounts of water at the expense of maximum methyl lactate yield.",
author = "Irene Tosi and Anders Riisager and Esben Taarning and Jensen, {Pernille Rose} and Sebastian Meier",
year = "2018",
doi = "10.1039/C8CY00335A",
language = "English",
volume = "18",
pages = "2137--2145",
journal = "Catalysis Science & Technology",
issn = "2044-4753",
publisher = "Royal Society of Chemistry",
number = "8",

}

Kinetic Analysis of Hexose Conversion to Methyl Lactate by Sn Beta: Effects of Substrate Masking and of Water. / Tosi, Irene; Riisager, Anders; Taarning, Esben; Jensen, Pernille Rose; Meier, Sebastian.

In: Catalysis Science & Technology, Vol. 18, No. 8, 2018, p. 2137-2145.

Research output: Contribution to journalJournal articleResearchpeer-review

TY - JOUR

T1 - Kinetic Analysis of Hexose Conversion to Methyl Lactate by Sn Beta: Effects of Substrate Masking and of Water

AU - Tosi, Irene

AU - Riisager, Anders

AU - Taarning, Esben

AU - Jensen, Pernille Rose

AU - Meier, Sebastian

PY - 2018

Y1 - 2018

N2 - Simple sugars bear promise as substrates for the formation of fuels and chemicals using heterogeneous catalysts in alcoholic solvents. Sn-Beta is a particularly well suited catalyst for the cleavage, isomerization and dehydration of sugars into more valuable chemicals. In order to understand these processes and save resources and time by optimising them, kinetic and mechanistic analyses are helpful. Herein, we study substrate entry into the Sn-Beta catalysed methyl lactate process using abundant hexose substrates. NMR spectroscopy is applied to show that the formation of methyl lactate occurs in two kinetic regimes for fructose, glucose and sucrose. The majority of methyl lactate is not formed from the substrate directly, but from methyl fructosides in a slow regime. At 160 °C, more than 40% of substrate carbon are masked(i.e. reversibly protected in situ) as methyl fructosides within few minutes when using hydrothermally synthesised Sn-Beta, while more than 60% methyl fructosides can be produced within few minutes using post synthetically synthesised Sn-Beta. A significant fraction of substrate thus is masked by rapid methyl fructoside formation prior to subsequent slow release of fructose. This release is the rate limiting step in the Sn-Beta catalysed methyl lactate process, but can be accelerated by the addition of small amounts of water at the expense of maximum methyl lactate yield.

AB - Simple sugars bear promise as substrates for the formation of fuels and chemicals using heterogeneous catalysts in alcoholic solvents. Sn-Beta is a particularly well suited catalyst for the cleavage, isomerization and dehydration of sugars into more valuable chemicals. In order to understand these processes and save resources and time by optimising them, kinetic and mechanistic analyses are helpful. Herein, we study substrate entry into the Sn-Beta catalysed methyl lactate process using abundant hexose substrates. NMR spectroscopy is applied to show that the formation of methyl lactate occurs in two kinetic regimes for fructose, glucose and sucrose. The majority of methyl lactate is not formed from the substrate directly, but from methyl fructosides in a slow regime. At 160 °C, more than 40% of substrate carbon are masked(i.e. reversibly protected in situ) as methyl fructosides within few minutes when using hydrothermally synthesised Sn-Beta, while more than 60% methyl fructosides can be produced within few minutes using post synthetically synthesised Sn-Beta. A significant fraction of substrate thus is masked by rapid methyl fructoside formation prior to subsequent slow release of fructose. This release is the rate limiting step in the Sn-Beta catalysed methyl lactate process, but can be accelerated by the addition of small amounts of water at the expense of maximum methyl lactate yield.

U2 - 10.1039/C8CY00335A

DO - 10.1039/C8CY00335A

M3 - Journal article

VL - 18

SP - 2137

EP - 2145

JO - Catalysis Science & Technology

JF - Catalysis Science & Technology

SN - 2044-4753

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